Five-time singles champion Williams, a mixed doubles finalist with Bob Bryan at Wimbledon 16 years ago, has been troubled by a leg injury in recent months.
But the 42-year old was determined to be involved at this year’s Championships and the pair have been drawn against Alicja Rosolska and Michael Venus in the first round.
“The mixed can be so random but I’m just excited about playing with Venus,” said two-time mixed doubles champion Murray, whose brother Andy has previously played with Serena at SW19.
“I wasn’t planning on playing but what can you do when Venus calls?
“She asked me last year but my neck had been so bad and I just wanted to concentrate on the men’s doubles. When she asked me again this year I didn’t realise this would be her only event here and you can’t say no to Venus twice can you?
“It’s going to be a great experience to be on the court with such a champion. I’m really looking forward to it, it’ll be great fun win or lose.”
Murray and long-time partner Bruno Soares started their men’s doubles campaign with a straightforward and straight sets win over France’s Benjamin Bonzi and Arthur Rinderknech, progressing 6-3 6-4 6-2.
The pair are seeded nine and Murray admits he takes pride in seeing so many other British players among the seeds here, including Joe Salisbury, Neal Skupski and Lloyd Glasspool.
“I think I made a lot of the guys aware that you can have a good career in tennis playing doubles, it doesn’t have to be singles or nothing,” he said.
“I supported some of those guys when they were lower down the rankings and finding their way in doubles.
“In truth the biggest contributor is having Louis Cayer in charge of men’s doubles in the UK. It’s not a surprise we have so many players at the top of the game when we’ve got the best doubles coach in the world working for us.
“I know how much work he’s done with those guys. What he’s done is super impressive, there isn’t anyone else in the world with his record.”
Salisbury and American partner Rajeev Ram beat Murray and Soares at Queen’s Club this month - and are tipped as the ones to watch this fortnight.
“We got off to good start to each set and we just established a momentum that got us through, we did a good job of controlling things,” added Murray.
“We lost in two tie-breaks at Queen’s against the number one seeds here, so we’re playing good tennis but Wimbledon is obviously another level.”
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