In three previous visits to the Stade Pierre de Coubertin, Pavlyuchenkova has never been beyond the second round and she looked set for another early exit when she dropped a one-sided opening set in just 27 minutes.
At the start of the second set, though, the Russian gained a belated foothold in the match and forced a decider when she broke Schiavone to love in the final game. It was a setback from which the Italian never recovered, Pavlyuchenkova rattling off the first five games of the third set as she eased to a 16 64 61 victory.
The opening day's only other main draw match saw Klara Zakopalova bring an early end to the hopes of French wildcard Caroline Garcia. Two years ago, Zakopalova reached the semifinals in the French capital, and following a topsy-turvy opening set she eventually ran out a comfortable 76(4) 62 winner to book a second round meeting with No.4 seed Angelique Kerber.
Tournament directors Régis Brunet and Amélie Mauresmo have done an excellent job in attracting a star-studded field to this year's tournament, with Maria Sharapova, Petra Kvitova and Kerber leading the way.
All four have enjoyed success at the venue in the past, and it holds particularly special memories for Kerber, who won her first WTA title here two years ago. The German arrived in Paris a week ago and is feeling upbeat about her chances.
"I've been here one week already so I've had some practice indoors and I'm feeling good," Kerber said at Monday's All-Access Hour. "Of course, in Australia it was very hot and it's nice to be back and have the change - I love Europe and even the snow!
"I think I had a great start to this year - I reached the final in Sydney and in Melbourne I was also playing good tennis. I'm always improving and all the time looking forward to my next matches and next tournaments."
"It took some time to get over," Kvitova said. "But it was only one match and I think I played well before that and hopefully I can get that winning feeling back here.
"I have good memories from this tournament and I hope these memories help me this year.
"I don't really think I need to change something - I worked hard in the off-season on my serve and my fitness - it was just unlucky for me that I couldn't show it at the Australian Open. The work that I did is still there and I just need some matches now."