Britain's Murray, who won singles gold in 2012 and 2016, will play only in the doubles before he retires while Djokovic could meet record 14-time French Open champion Rafa Nadal in the second round.
With Roger Federer putting his feet up after retirement in 2022 and Nadal also nearing the end of a long and glorious career, the job of prolonging the 'Big Four' era falls squarely on Djokovic's shoulders.
"I hope that Andy will have the best possible farewell in his last competitive match here in Olympics, for him and his country.
"He is a legend of our sport, he has been an incredibly important player for tennis globally," Djokovic said.
"Nadal, the same, even more so with all the results and achievements he has had, particularly in this city, in Roland Garros.
"He still didn't say when his last tournament will be, so hopefully for the sake of the sport, he can keep going.
"I don't have retirement on my mind even though I know a lot of people would love me to retire so that this era is done. But I think as long as there is at least one of us left, I think the era is still going."
On a potential duel with Nadal, Djokovic said: "It will surely be a spectacle, like the good old days when we played on more or less all the big tennis courts around the world.
"I'm also excited for that eventual duel, but I have to overcome the first obstacle and do my best to go as far as possible."
Djokovic described youngsters Carlos Alcaraz and Jannik Sinner as the two best players in the world who will "carry the sport into the future" but that was not going to stop the Serbian from striving to win titles.
"I've been present for the shift of many generations in the last 15 years," added Djokovic, who lost to Alcaraz in the Wimbledon final earlier this month.
"The end is nearer than the beginning, but I still enjoy competition and I'll keep going until I don't enjoy it anymore."
Djokovic has not won a title this year and having pulled out of the French Open before the quarter-finals for knee surgery, he has unfinished business at Roland Garros, even if his preparation has been far from ideal.
"This year we haven't had time to prepare properly because the tennis calendar was very busy. I played Wimbledon because it's the most important tournament in our sport and it is also a softer surface, so it gave me time to adapt with my knee injury.
"I also haven't had a proper preparation before Wimbledon, but in the last four to five days, I have felt more ready for the Olympic Games than I have for Wimbledon."