The 23-year-old will face 11th seed Paola Suarez in tomorrow's quarterfinal after the Argentinian beat Rita Grande 4-6, 6-0, 6-2.
The winner of that match would expect to face Serena Williams in the semi-finals but Mauresmo would even approach that match with more confidence than most.
She has beaten the defending champion in the past and achieved a rare double last year by being the only woman to beat both Williams sisters.
Fears for the 16-year-old Golovin on Centre Court seemed well-founded as the French girl quickly went 3-0 down to top seed Williams. The six-times Grand Slam champion was in great form, hammering ground strokes that wrong footed the 5ft 9ins youngster, but there was a dramatic turn around in the fourth game.
Golovin, who won the mixed doubles title with Richard Gasquet at the French Open, held serve with real power and then delighted the Centre Court crowd by breaking the defending champion in the next game.
Williams, watched by her mother, played a loose game, netting a simple smash volley and then making a backhand error to prove she was some way from top form after just five tournaments since her knee operation.
At least the loss forced the champion to work harder and Williams immediately broke back and then put real pressure on Golovin who was serving to stay in the set. A delicate drop shot had Williams thundering towards a ball boy who managed to take evasive action.
However, another error brought a squeal from Golovin as she faced a set point and a big back hand down the line flew well wide to hand Williams the set 6-2 in 28 minutes.
She made even shorter work of the second set, racing to 6-1 and barely breaking sweat.
Jennifer Capriati, the seventh seed , took the initiative in her fourthround-clash against Russian Nadia Petrova by winning the first set 6-4.
But the experienced American had to work desperately hard for her points against the 13th seed.
Capriati failed to take advantage of seven break points in the fifth game in a baseline battle.
But the 28-year-old American set up an eighth break point in the same game with a superb cross-court passing shot. She then went 3-2 ahead when Petrova hit a forehand into the net in the next rally. Capriati served well to stretch the lead to 4-2. But in the next game the American failed again to capitalise on another three breaks points as 21-year-old Petrova refused to crack under pressure.
The Russian broke Capriati's serve to level at 4-4 when the American hit a backhand out of court.
Capriati managed to break back straight away when Petrova hit a backhand approach shot out of court.
The American then clinched the set with a fortunate forehand which hit the net cord on its way over.
