PSG are favourites to win back the league title this season, but it is the Champions League that takes priority for Unai Emery's men.
Nene revealed that he talked to Neymar a lot in the build up to his move and was delighted to see him take the club's No.10 jersey that the current Vasco de Gama player wore himself at Parc des Princes.
According to the 36-year-old, a first ever European crown is inevitable after their recent second round and quarter-final eliminations.
"Neymar is a real buddy, and seeing him in my old team with my old jersey is fantastic," he told Le Parisien.
"We talked a lot before he signed. I weighed the pros and cons, but I told him that Paris was the best choice for him. This is where he can become the best player in the world, where he can write the story. Paris has never won the Champions League and it is a challenge.
"Not much was missing from the last two or three years. Last season they beat Barca 4-0!
"With the contribution of Dani Alves and Neymar, it is quite doable. I even think they can win it this year. I'm really glad Neymar made that choice, he will not regret it."
It was not all an easy decision for Neymar, however, who had enjoyed success as part of Barca's incredible attacking line-up alongside Lionel Messi and Luis Suarez.
Nene continued: "I went back home on holiday to Angra dos Reis [near Rio de Janeiro]. He (Neymar) has a house by the sea. He can't go out of his house, otherwise it is madness, so he has to stay locked up a bit. But we had fun, we played basketball, football, video games.
"It was at this time that he was in full doubt and that he was hesitating between Paris and Barca. Afterwards, when he returned to Barcelona, it was difficult. Lionel Messi, Gerard Pique, Luis Suarez, the leadership, everyone put pressure on him to stay.
"It was not easy to manage, you have to put yourself in his place. He had doubts and that's normal, but he was brave. I think he managed it well, thanks to his father. It was he who had a headache with this transfer. Neymar stayed cool with it. He has not lost his love of live or football."
The world-record fee PSG paid to sign the 25-year-old has sparked immense controversy in world football, as has the reported €30m per year contract he is on. However, Nene is sure Neymar is worth the money and does not expect any jealousy to develop in the changing room.
"It's not Neymar's fault that his transfer was so costly," he said. "I think every player is happy with the salary he is getting and no one is going to be jealous of Neymar's salary.
"He deserves what he earns. He is the future best player in the world. In addition, he is cool with it, he is simple with everyone, so there will be no worry."
On Neymar taking the No. 10 jersey at PSG, Nene added: "He did not know whether to ask the 10 or 11. But I said: 'You're crazy, you have to take 10!' We played the video game Counter-Strike together and we talked about that. I wanted to see him in the No.10, not 11.
"We must also thank Javier Pastore for giving up his number."