The Scot has been in impressive form since reversing his decision to skip the clay court season by accepting a wild card entry for the tournament in the Spanish capital.
Murray – currently ranked 78 – disposed of Dominic Thiem in straight sets in the opening round. He then claimed a three-set win over Denis Shapovalov in the second round, downing the world No 16 from Canada 6-1 3-6 6-2 having only lost his serve once in one of his best performances since having his hip resurfaced.
Murray, 34, only decided to play the event on clay two weeks ago, but it is proving a shrewd move as he prepares for a mouth-watering third-round tie against Djokovic.
The duo last played in 2017 in final of the Qatar Open in Doha, which Djokovic won in three sets. The rivals have known each other since they were children and faced-off 36 times in their professional careers.
The Serbian booked his last-16 spot with a win over Gael Monfils, with his match against the Scot set to take place on Thursday morning.
Here is everything you need to know about the match...
When is Andy Murray’s next match?
Andy Murray will take on Novak Djokovic in the last 16 of the Madrid Open on Thursday, May 5, at 11am UK time.
The tournament is held at Caja Magica in Madrid, an outdoor arena with a retractable-roof equipped main court.
Dusan Lajovic or the winner of Hubert Hurkacz vs Alejandro Davidovich Fokina await in the quarter-finals.
What channel is Andy Murray v Novak Djokovic on?
Andy Murray’s match against the world number one will be broadcast live on Amazon Prime Video. You can sign up for a free 30-day trial.
Afterwards, a subscription costs £7.99 a month and offers free next day delivery on items ordered from Amazon, as well as the Amazon Prime Video library.
You can live stream the tennis from your phone or tablet or any smart device with the Amazon Prime Video app.
What has Andy Murray said ahead of the match?
"He's the world number one and I've got a metal hip," Murray told Amazon Prime.
"I didn't know I'd get opportunities to play matches like this again. In theory I shouldn't have a chance in the match.
"But I've worked my hardest, put myself in a great position and it's a fantastic opportunity to play against him again on a big court in a huge tournament."
Andy Murray v Novak Djokovic odds
Novak Djokovic (1/7) Andy Murray (9/2) – Bet365