And the 20-time grand slam victor, who will attempt to win a third straight Australian Open title later this month, was satisfied with where his form and fitness is at.
Playing in front of the highest single session attendance in the tournament's history, the team of Federer and Belinda Bencic beat Williams and Frances Tiafoe 4-2 4-3 (3) to clinch the tie to top the group.
However, even a rare defeat couldn't take the gloss off the experience of facing Federer for the first, and nearly certainly the only, time.
"It's just very exciting for both of us", Federer said about the match.
"It is going to be one time, probably never again".
"I really enjoyed playing against Serena, what an honour and pleasure", he said.
"I admire everything she's done on and off the court".
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Federer faced three break points in his first service game, but was near flawless from that point on as he wrapped up the contest in 57 minutes at RAC Arena on Sunday night.
Federer won seven games in succession and eight of the last nine as Tiafoe dropped away.
Speaking at the Gala, Serena spoke about the difficulties of being a parent and called Federer "Superman" for being a father to twins.
"It's about staying fit and healthy and managing the game day by day".
Williams and Bencic followed the men on court for the women's singles. I made the serve, but I totally missed the target - thank you for missing the ball.
Tiafoe stayed with Federer until the 12th game of the first set when the Swiss broke to win the first set.
"It was such a quick turnaround (from yesterday's match)", Williams said.
"I've played with some of the greatest doubles players in the world in Martina Navratilova and Martina Hingis, and I've also played against some of the best in Venus and other great ones in the past".
Defending champions Switzerland sealed a 2-1 victory over six-times winners United States that left them bottom of Group B but the result mattered little to over 14,000 fans in Perth and millions around the world who had eagerly awaited the contest.