The former world No 1 will team up with Murray after Martina Hingis, with whom the Scot won the title last year, retired from the game.
Murray – a five-time grand slam doubles champion – was sought out by Hingis last year, but it was roles reversed this time and Azarenka is flattered.
Asked how it felt to be pursued, the Belarusian said: “Special. I don’t really think of it this way, but I think he has pressure he has to defend.
“I’ve got nothing to defend. So I’m just going to enjoy it.
“I’m very much looking forward to having English people on our side and being hopefully a crowd favourite for the first time in England.
“Jamie is an amazing player. To see how much he has progressed over the years and making a big name for himself is really cool.
“So I’m excited to play with him. But he actually asked me. I was thinking about doubles or mixed doubles or something to play, and he reached out to my coach and I said yes.”
Murray initially said he would miss the mixed event to focus on the men’s doubles with Brazilian partner Bruno Soares but has now changed his mind.
“I wasn’t actually planning on playing and then I spoke to her coach about it yesterday and she was looking for a partner,” Murray told the Wimbledon Channel. “So I thought, ‘Yeah, let’s go for it’. She’s a great player, she’s had so much success and it’s a great opportunity for me to play with someone as good as her.”
Azarenka, 28, has won the Australian Open singles title twice but is now ranked 87th in the world. She lost to Karolina Pliskova in the second round of the singles at Wimbledon yesterday.
Murray and Soares are seeded fifth in the men’s doubles.