The pair have never met on a tennis court but the top seed knows she will have her work cut out.
Golovin reached the quarter-finals of the Australian Open in January as a 15-year-old schoolgirl and has the bit firmly between her teeth here on Wimbledon's grass.
"She's been doing really well. I saw her play at the French Open, actually," Serena said.
"I've been watching her game a little bit."
The American champion says she is playing better than when she won the title last year.
"Actually, I'm feeling better," she said. "I've been through a lot physically, you know? Right now I'm really, really, really feeling good for the first time."
Golovin won the mixed doubles at the French Open earlier this month but it has been on the green grass of England that she has nurtured her game.
In Edgbaston earlier this month she stormed to the final only to lose to Maria Sharapova.
She is looking forward to a tilt at Serena.
"I'm already very excited to be in the fourth round," she said. "Playing Serena is going to be amazing.
"It's my second time playing against somebody in the top 10. I'm just really excited."
Golovin, born in Russia and raised in France, says she loves playing on grass.
"You know, I played well in Juniors here," she said. "I played very well in Birmingham. This surface suits my game, so it's going well."
Fellow former champion Lindsay Davenport also features, playing the conqueror of Venus Williams, Karolina Sprem.
"She hits some big shots," Davenport said. "It's going to be a tough baseline match."
Preceding Davenport on court one will be fellow former world number one Jennifer Capriati. The American takes on Russia's Nadia Petrova for a place in the quarters.
Fourth seed Amelie Mauresmo takes on Silvia Farina Elia, Ai Sugiyama and Maria Sharapova clash and Paola Suarez's match with Rita Grande completes women's fourth round action.
