The Liverpool man started in tandem with Declan Rice in midfield at the Veltins-Arena, where England won their first match of a major tournament for the fourth time in a row under Gareth Southgate.
Jude Bellingham's first-half header was the difference in Gelsenkirchen, although England had to weather a Serbian storm for the best part of an hour as Dragan Stojkovic's side tried in vain to claw their way back into the contest.
The Three Lions did have the best chance of the second 45, as a Harry Kane header smacked Predrag Rajkovic's gloves and bounced off the crossbar, but Southgate's men still emerged victorious despite not being at the races after the break.
For all of his successful exploits as a defender for Liverpool, Alexander-Arnold is often deployed in midfield for the Three Lions, partially down to Kyle Walker nailing down the right-back spot under Southgate.
Alexander-Arnold lifts lid on "demanding" midfield role
However, the England boss has also stressed that he is keen to add a new passing dimension to his engine room with the inclusion of Alexander-Arnold, who shone in such a role in the recent friendly win over Bosnia-Herzegovina.
The 25-year-old beat Conor Gallagher, Adam Wharton and Kobbie Mainoo to the second midfield spot on Sunday, where another competent display saw him complete four long passes from six attempts and make two interceptions, one tackle and one clearance.
Speaking to englandfootball.com after England's victory, Alexander-Arnold opened up on his new role for his country and gave special credit to Holland for helping him to adapt to the demands of the position.
"It's physically demanding but when you're playing with the likes of Declan, Jude and the others in and around you with an experienced back four behind you, it helps. With Declan and Jude talking to you and guiding you through it, it's hard to go wrong," Alexander-Arnold said.
"The manager and the staff, Steve Holland especially, we've put a lot of work into this role. So I was well prepared and I knew what was asked of me and what role I needed to do and hopefully they felt like I executed it because we got the win in the end."
Alexander-Arnold praises Holland after purported Ben White comment
Alexander-Arnold's praise for Southgate's right-hand man comes after accusations that Holland made a cutting comment to Arsenal's Ben White, who left the 2022 World Cup camp for personal reasons and has not played for his country since.
In November 2023, Southgate was asked about White's frequent omissions from the England squads, stating that several players were "ahead" of the Arsenal man despite his impressive form in North London.
However, the England boss subsequently revealed in March that White had made himself unavailable for selection amid reports that the right-back had taken offence to a Holland remark about his interest in football at the World Cup.
Southgate has vehemently denied that such an interaction took place, though, and the England boss now has three days to prepare his side for Thursday's encounter with Denmark, where they could seal top spot with a game to spare by taking all three points.