Djokovic leads the head-to-head 25-11 but Murray claimed memorable victories over him to win the US Open in 2012 and Wimbledon a year later.
He did, however, lose to Djokovic in the Melbourne showpiece in 2011, 2013, 2015 and 2016, and also lost the French Open final in 2016.
Murray replaced Djokovic as world number one at the end of the 2016 season, going on a 24-match winning streak to end the year, but a hip injury a year later would ultimately impact his career.
Murray announced in the summer that the Paris Olympics would be his last tournament, and he made it to the quarter-finals of the men’s doubles alongside Dan Evans before bowing out.
“I’m going to be joining Novak’s team in the off-season, helping him to prepare for the Australian Open,” Murray said.
“I’m really excited for it and looking forward to spending time on the same side of the net as Novak for a change, helping him to achieve his goals.”
Djokovic made changes to his team this year, including parting ways with long-time coach Goran Ivanisevic.
The Olympic medal was the only title he won in 2024 and he ended his season early after sustaining an unspecified injury.
It is the first season since 2005 in which he has not won an ATP event, and only the fourth since 2008 in which he has not won one of the four Grand Slam titles.
“I look forward to starting the season with Andy and having him by my side in Melbourne, where we’ve shared many exceptional moments throughout our careers,” Djokovic added.
