The Stormers saw off Bristol Bears 49-12 at the DHL Stadium to get their campaign off to a good start.
De Villiers stepped in for regular captain Ruhan Nel, who was ruled out of the match with a calf injury and this milestone marks an already remarkable year for the former Junior Bok captain who made his Springbok debut against England in July.
De Villiers says the win also provided an opportunity to learn.
"Yeah man, pretty happy about it, I look to my left there's a Springboks captain and to my right there's Evan Roos.It was an easy one to start with but yeah we can't complain. In the first Champions Cup game, few guys got an opportunity, bonus point win and we got an opportunity to learn from them,” de Villiers said.
“So, I mean you always wanna learn and if you can learn well, winning and doing well, that's awesome, so really happy."
The 23-year-old, who came through the Western Province academy system, admitted that he sometimes lost patience while waiting for opportunities in the first team.
However, he stressed the importance of remaining patient as well as being present in the moment.
"I think there were stages moving up to this where I lost a bit of patience, as a youngster you wanna play, you wanna be on the field. I obviously got through the ranks, I think I played every junior rugby game there was but that was massive for me, that's probably why I can sit here today,” he added.
“I would say being present in the moment, that U20 game at City Park, be in the moment and give your best because one day or two years later, it's a different story, so yeah."