The 24-year-old midfielder completed his £105million switch from West Ham on Saturday and just four days later made his bow 3,660 miles away from the Emirates Stadium.
Rice was introduced as a second half substitute in Washington DC as Arsenal swept aside the Rooney-managed MLS All-Stars 5-0 in sweltering conditions.
Gabriel Jesus’ audacious clipped effort gave the Gunners an early lead that Leandro Trossard added to with a lasered effort from the edge of the box.
Jorginho’s penalty, a fine Gabriel Martinelli finish and Kai Havertz’s first goal in an Arsenal shirt completed the win on a night when new boys Jurrien Timber and Rice made their first appearances for the club.
There was a hearty Arsenal contingent at Audi Field, where director Josh Kroenke received a warm cheer before Rooney, the Manchester United and England great, was jeered.
The Gunners supporters in attendance only had to wait five minutes before celebrating a moment of magic.
The All-Stars appeared to have stopped a dangerous attack, only for Jesus to meet a loose ball with an audacious clipped effort from the edge of the box that curled in off the far post.
Rooney’s side responded with determination but were unable to unlock the visitors, who extended their lead midway through the first half.
Bukayo Saka was sent behind down the right and passed across to Trossard, who cut away from his man and scored a thumping right-footed drive from 22 yards.
Arsenal’s opening goalscorers nearly combined for a third soon after but Jesus could only head Trossard’s deep cross into the side netting.
Impressive Trossard sent a free-kick just wide before an opening period that somehow featured five bookings was called to an end.
Within seconds of the restart a Tim Parker handball gave Arsenal the chance to score a third.
Jorginho scored the resulting spot-kick and the Gunners will be hoping Trossard avoided any major issue after limping off in the 55th minute.
Referee Ted Unkel did not award another Arsenal penalty despite the VAR advising him to review a decision, instead indicating for the visitors to make their planned substitutions.
Timber came on for his first appearance and Rice received the biggest cheer.
Arsenal continued to control proceedings and Martinelli coolly struck home in the 84th minute after being played in by an excellent Martin Odegaard pass.
Havertz completed the one-sided victory when controlling and finishing from close range in the 89th minute.
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