Mladenovic, who won the mixed doubles title at the All-England Club alongside Daniel Nestor, had some tough moments in the second set - she was down 5-2, and had to fight off six set points down 5-3 - but the No.3-seeded Frenchwoman toughed it out and edged the Portuguese qualifier, 61 76(5).
"It's difficult to adjust to the conditions here - it's much different here than Wimbledon, obviously," Mladenovic said. "Going from grass courts and the London weather to clay and the weather here, I've been struggling, but I'm happy to win my first match and overall I'm happy with the way I'm playing."
The conditions haven't been the only curveball for Mladenovic - the trip here was a whirlwind.
"We played our mixed doubles final after the men's final on Sunday and it was 8-6 in the third set - but it didn't finish until 8:30. Then I had press and other things, then we had to get dressed for the ball, so we got there pretty late. But on top of that, there was only one direct flight to Palermo, and it left 6am on Monday morning, and we had to be there by 4am, and for that we had to leave around 2am, so basically we were dancing, then went back, got a taxi at 2am and then waited at the airport!
"When I got to Palermo I was exhausted."
Mladenovic was also in the player box for Marion Bartoli's singles triumph at Wimbledon - the next day, Bartoli returned the favor, sitting in the player box for Mladenovic's mixed doubles championship.
"We were very proud of each other - the French men have been doing so well for so long, so by getting to the finals there, and then winning, we proved that we can do it too. We've been working so hard and waiting for our time, and it came. I could really feel the emotions during Marion's final - and it's so nice of her to come and watch my final there the next day. She's really a very good friend of mine.
"It's just unbelievable to have my first Grand Slam title, and everything that has happened the last few days is such a great experience. I hope I can continue this momentum in Palermo this week!"
That was the last first round match of the week - the second round also kicked off, with No.1 seed Sara Errani the most notable winner, beating Barbora Zahlavova Strycova in a rematch of last year's final, 63 62. It was Errani's 38th WTA match win of the year, breaking a tie with Maria Sharapova for second-most WTA match wins of the year - Serena Williams leads that leaderboard with 46 victories.
No.7 seed Sílvia Soler-Espinosa, Dinah Pfizenmaier and Renata Voracova also made the quarterfinals - in fact, for the 21-year-old Pfizenmaier it will be the first WTA quarterfinal of her young career.