Seven-time singles champion Williams will play at the All England Club for the first time in four years after being handed a wild card into the main draw.
The 44-year-old mother of two is also set to partner elder sister Venus, 46, in the women's doubles competition.
Djokovic, a fellow seven-time singles champion at SW19, said: "First and foremost, what she's doing is inspirational and it's epic. That's what I told her.
"I always admired her career, her journey, her story. Of course, Venus' as well.
"For her to come back after years of being absent from the tour, two children later, and to give so much effort to, not just for her own satisfaction or coming back on the tour, but also to give all of us a pleasure of seeing her back on the court is remarkable.
"I told her that whatever happens, what she's doing is truly inspirational for me personally – I'm sure for millions around the world."
Williams, who has won a record 23 women's major singles titles in the Open era, will take on Australian world No.53 Maya Joint in the first round.
She and five-time Wimbledon singles champion Venus have been drawn to face Colombian Camila Osorio and Argentinian Solana Sierra in the doubles.
"I see her in the gym more than I have seen her when she was at her prime," said Djokovic. "It tells me that she really wants this to work out the best way possible.
"It's admirable, honestly, the effort she's putting in. Of course, all eyes are on her, her comeback. I just hope that she will enjoy because she really deserves (to).
"She created something historical, legendary in her career. She deserves every applause she's going to get."
Amid the rise of Jannik Sinner and Carlos Alcaraz, Djokovic won the last of his seven Wimbledon crowns four years ago, with the most recent of his record 24 major titles coming at the 2023 US Open.
He suffered a third-round defeat to Joao Fonseca last month at the French Open but hopes to peak in south-west London following a recent shoulder issue.
"I think I'm better prepared here than I was for Roland Garros," said the 39-year-old, who begins against China's Wu Yibing.
"Obviously playing on grass, comparing to clay, you don't need to exert as much physical effort, so that's better for me.
"I always loved playing on grass. I have a very good history in Wimbledon. That gives me a higher dose of confidence coming into the tournament.
"Roland Garros was physically very draining, demanding. Three matches that I played, all of them went almost four hours. But I'm proud of the effort
"Anyway, I was planning to peak at Wimbledon after the injury of the shoulder that kind of kept me away from the tour for several months.
"Hopefully I'll have a good tournament here."
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