Madrid hold a 3-1 lead from the first leg of the last-16 tie at the Santiago Bernabeu last month, while PSG must do without Neymar due to the Brazilian superstar's broken metatarsal.
While Neymar joined for a world-record €222million in August, his compatriot Alves made the move to Parc des Princes on a free transfer after securing his release from Juventus.
It means the 34-year-old was not around when Neymar inspired Barcelona to a 6-5 aggregate win over PSG at this stage of the Champions League last season, despite losing 4-0 in Paris.
Progressing through such ties is a must, according to Alves, if PSG are to prove vast Qatari investment has produced a team of genuine substance.
"What are PSG missing? Matches like this to show that Paris is not all about money," the former Barca favourite said at a pre-match news conference.
"I came here because I am a competitor – it's in my blood. And being part of the history of the club isn't something you can buy.
"If I speak to the squad, I'll say we have to seize this important moment. History is there to be changed.
"Changing history was one of the big reasons I came here and now we have to do it. We can't even think about it – we just have to do it. And we believe we can.
"We think we can go through because of the first leg. We were superior to them in our play and the chances we created.
"We have to do that for the full 90 minutes this time. It's a huge motivation to be able to knock out the holders."
Despite such rousing, bullish talk, Alves acknowledges Neymar's absence is bound to be felt by Unai Emery's side.
The 26-year-old underwent surgery at the weekend and even though Brazil have predicted a lay-off of up to three months, Alves is determined to give his friend the chance to sample Champions League football once more this season.
"It's impossible not to feel the absence of a player like Neymar," he added. "But either you cry or you get on with it, and I choose the second option.
"I speak with him practically every day and we've said we'll meet again later in the competition."