Federer oozed class and authority against British nearly-man Tim Henman on Centre Court, chastening his friend and four-times semi-finalist 6-4 6-0 6-2 in a one-sided second round match.
Williams uncoiled her long limbs for the first time this year on grass, dismantling fellow American Bethanie Mattek 6-1 6-0 to reach the second round.
Monday's rain meant sixth seed Williams, along with world number one Amelie Mauresmo and 2004 champion Maria Sharapova were playing catch-up in the draw.
Mauresmo hit the ground running, recording a 'double bagel' 6-0 6-0 demolition of hapless Croatian qualifier Ivana Abramovic while Sharapova reached round two with a ruthless 6-2 6-0 defeat of Israel's Anna Smashnova.
"It's one of the great matches that I've played here," Mauresmo told reporters, although her 38-minute victory constituted little more than a glorified knock-up.
If that trio barely broke sweat, Belgian second seed Kim Clijsters did not even hit a ball, moving into the third round courtesy of a walkover against ill Ukrainian Viktoriya Kutuzova.
Clijsters was joined by fellow Belgian Justine Henin-Hardenne and 1997 champion Martina Hingis, who continued to look at home on her first visit since 2001.
Hingis beat Tathiana Garbin 6-1 6-2 in fading evening light while French Open champion Henin-Hardenne outclassed Russian Ekaterina Bychkova, also for the loss of just three games.
Henman, unseeded for the first time in 10 years at his beloved Wimbledon, fancied his chances of ending Federer's march towards a fourth consecutive title while the Swiss even admitted to apprehension at facing such a renowned grasscourt exponent so early in the tournament.
What transpired was a very public tennis lesson for Henman with Federer gaining revenge for his defeat by the 31-year-old five years ago on the same Centre Court.
From 5-4 in the opening set Federer launched an 11-game barrage that had Henman reeling and his fans watching on in macabre fascination. Federer's match-clinching ace came as a blessed relief.
"It's not a lot of fun beating a friend like this, that's for sure" said Federer, who still trails Henman 6-5 in head-to-heads.
"It's difficult to be happy about the whole thing because you know (the fans) are not really enjoying it and Tim obviously was not."
FEDERER EXPRESS
It was bad for Henman, and not pleasant viewing for third seed Andy Roddick and 2002 champion Lleyton Hewitt, two of those annually saddled with trying to derail the Federer express.
A fretting Roddick, runner-up the last two years, had enough problems scrambling into the second round past tenacious Serb Janko Tipsarevic 6-7 6-4 7-6 6-2.
Hewitt, at least, looked in fine fettle, trouncing Italian Filippo Volandri 6-1 6-1 6-3 in his delayed first round match.
"It was a nice one to get under my belt. Especially knowing you have to back it up again tomorrow in the second round," said the 25-year-old Hewitt.
Both will have to play their second rounds on Thursday, as will Croatia's fifth seed Ivan Ljubicic who narrowly survived a five-setter with Spain's Feliciano Lopez, coming through 6-3 6-4 5-7 3-6 11-9.
David Nalbanian, the burly Argentine fourth seed, joined Federer in the last 32 after his second straight sets victory, this time over Frenchman Arnaud Clement.
Williams has played in only four tournaments this year because of arm and elbow injuries but the 26-year-old shook off any rust to give the 103rd-ranked Mattek the runaround.
"She looked cute," said Williams afterwards, referring to 21-year-old Mattek's decision to play in what looked like fancy dress, complete with 1970s-style knee length white socks, tight shorts and bandana.
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