Hill was leading when the field took the green with 11 laps of 79 remaining, at which point the New Zealander got on his inside as they climbed into Turn 2.
Contact ensued although, unlike their stoush at the Circuit of The Americas back in March, their latest incident appeared unintentional, with van Gisbergen kicking up the dirt on his inside before sliding wide and into the #21 Richard Childress Racing Chevrolet.
In any case, though, it gave the #97 Chevrolet a lasting lead and the Supercars champion is now a two-time Xfinity Series race winner, doubling his tally just a week after taking his first.
READ MORE: Hill refuses to be drawn into SVG controversy
He did it the hard way, too, losing track position when the #97 Kaulig crew opted to take the points for the Stage 1 win rather than pit early with an eye to Stage 2, then having to deal with a voltage problem during Stage 3.
Sheldon Creed finished 1.323s back in second place in the #18 Joe Gibbs Racing Toyota, with Sam Mayer third in the #1 JR Motorsports Chevrolet.
Van Gisbergen had taken a career-first NASCAR pole position earlier in the day and duly led the field up the hill for the first time, ahead of JGR’s Ty Gibbs (#19 Toyota) and Kaulig’s other road course specialist, AJ Allmendinger (#16 Chevrolet).
Hill (#21 Chevrolet) wrested fourth from RCR team-mate Jesse Love (#2 Chevrolet) as they rounded Turn 7 while series leader Cole Custer (#00 Stewart–Haas Racing Ford) was 11th at the end of Lap 1 but first of the Mustangs.
Allmendinger dropped to fifth when he was passed by Hill on Lap 4 at Turn 11 then by Love on Lap 5 at Turn 7A, as van Gisbergen led by half a second.
Hill was more than five seconds away from the top two when he locked the rears and slid into the tyre barrier at Turn 11 on Lap 14, resuming in sixth once he was back up to speed.
Meanwhile, Custer had dropped to 13th after Chandler Smith (#81 JGR Toyota) nudged Parker Kligerman (#48 Big Machine Racing Chevrolet) into him at the same spot, a handful of laps earlier.
Gibbs was still just tenths of a second behind Car #97 when he pitted on Lap 18 to ‘flip the stage’ but van Gisbergen was told by Crew Chief Bruce Schlicker to stay out and bank the points.
With Love having also pitted, van Gisbergen won the 20-lap opening stage by 12.080s over Allmendinger, before they pitted in the break.
Gibbs filtered to the lead, from Love, Mayer, Justin Allgaier (#7 JRM Chevrolet), and Custer, with van Gisbergen eighth, Hill ninth, and Allmendinger 13th.
The race restarted on Lap 25 and Gibbs continued to lead, while van Gisbergen passed Custer for sixth at Turn 4 then Allgaier for fifth off Turn 7A.
He went under Creed a lap later at Turn 7A, at which point third-placed Mayer was about two seconds up the road.
The three-time Bathurst 1000 winner had caught Car #1 by Lap 37 but Mayer held him at bay at Turn 7A, and again at Turn 11 on Lap 39.
Van Gisbergen finally got the move done another lap later although Love had put a second on them by then, and leader Gibbs was a further four seconds to the good.
Mayer, and Hill from seventh, stopped on Lap 42 as the end of Stage 2 loomed, but van Gisbergen pressed on as he reeled in second-placed Love.
When Love ran wide at Turn 11 on Lap 43, metres after pit entry, van Gisbergen got a run and the RCR driver appeared to let him go as they approached Turn 1 again.
Gibbs won Stage 2 by 6.655s at the end of Lap 45 but the radio transmission to Car #97 suggested they were going to flip the stage and had been caught out by the #19 JGR fcrew not doing so.
Hill assumed the lead in the break, from Austin Green (#32 Jordan Anderson Racing Chevrolet) and Allmendinger, but, fortunately for Gibbs and van Gisbergen, most had not flipped.
Custer was quickest off pit lane and jumped to fourth but van Gisbergen was fifth, from Mayer and Creed, with Gibbs 14th after trouble changing the left-rear.
Stage 3 started with 30 laps remaining and hence a question over whether drivers could make it home on fuel, especially those who had flipped the stage.
Their cause was helped when an almighty mess unfolded as the field poured through Turn 3, causing the first unscheduled Caution of the day.
Jeb Burton (#27 JAR Chevrolet) and Chandler Smith had tangled, causing the latter to spin at the back of the top 10 and cars to spray everywhere, with Gibbs among those copping damage.
Under Caution, Hill led from Allmendinger and Green, with van Gisbergen having forced his way into fourth position as the incident unfolded behind them, Mayer holding fifth, and Custer sixth.
The restart came with 24 laps to go and van Gisbergen immediately picked off Green for third as they sped towards Turn 1.
When he arrived at Turn 11, he got down the inside of Allmendinger and muscled his way past.
The Kaulig team-mates did each other no favours while, right behind them, Custer was turned around by Mayer, who assumed fourth position.
Van Gisbergen struck trouble in the form of low voltage in the #97 Camaro and he fell more than a second behind Hill on Lap 62.
After being told what to switch off, he closed back in on the #21 Chevrolet before a Caution was called on Lap 64 in response to Love spinning at Turn 10.
Schlicker reported during the yellow that van Gisbergen “got it [voltage] back,” as he continued to circulate in second spot, ahead of Allmendinger, Mayer, Creed, Green, and Allgaier, with Custer 24th.
The fourth restart came with 11 laps to go and Hill initially cleared van Gisbergen as they arrived at Turn 1.
However, van Gisbergen had a look at Turn 2 and kicked up the dirt on the inside of the track before sliding into the side of the #21 Chevrolet and pushing Hill wide.
Van Gisbergen scampered away, ahead of Mayer and Green, before Allmendinger spun out of fourth when Creed locked the rears and clattered into him at Turn 7A.
Hill was back up to fifth spot on Lap 70 when John Hunter Nemechek (#20 JGR Toyota) slide wide off Turn 4, before Creed passed Green for third place on Lap 71.
Van Gisbergen led by 1.4s after Lap 72 and was two seconds to the good after three laps more, before Creed picked off Mayer at Turn 11 on Lap 76.
Spins for Ryan Sieg (#39 RSS Racing Ford) and Preston Pardus (#50 Preston Pardus Inc Chevrolet) raised the possibility of Overtime finishes but the race stayed green and van Gisbergen led by 2.234s at the white flag.
He cruised to the chequered flag, with Creed finishing second, from Mayer, Green, Hill, Allgaier, Chandler Smith, Nemechek, Custer, and Kligerman, while Allmendinger ended up 17th.
The Cup Series Race starts tomorrow at 15:30 ET/05:30 AEST.