The Paris Saint-Germain forward, who made his debut for his country in 2010, joins an exclusive club in reaching the century, moving up to joint-sixth on their all-time most-capped rankings alongside Robinho.
The 27-year-old is now the second centurion in the current squad, alongside defender Dani Alves, who moves on to 117 appearances after being named in the starting XI for the friendly clash in Singapore.
The other four players to have played over a hundred games include record-holder Cafu with 142, Roberto Carlos, Lucio and Claudio Taffarel.
Neymar, who sits third in his nation's all-time goalscoring list with 61, has the chance to go joint-second alongside Ronaldo if he finds the net against Senegal, with Pele at the top of the list with 77 goals.
Speaking ahead of the encounter with Aliou Cisse's side, the 27-year-old was effusive about reaching the milestone, adding that it was beyond all expectations he had for his career.
"For sure I've experienced some great things in previous years," he stated. "But you don't only have wins in your life when you're an athlete. You have to face disappointments, defeats, you make many mistakes.
"But if you are a persistent guy, if you fight and believe in yourself, if you can acknowledge your mistakes, in the end you can be a winner.
"So, to sum up, to reach these 100 caps is a big positive and I'm very happy with it. Not even in my best dreams I would imagine this could happen. God allowed things to be bigger and better than what I dreamt of."
Neymar became the world's most expensive player two years ago when he joined PSG from Barcelona for €222 million (£200m/$249m), while he was the subject of a protracted off-field saga this summer that saw him attempt to seal a return to Camp Nou.
Having struggled with injury throughout 2019, he has made five appearances so far this season for PSG, finding the net on four occasions.