Djokovic has qualified for the semifinals after winning his first two group matches at London's O2 Arena and Murray should also make the last four with two victories going into his last match against Stanislas Wawrinka on Friday.
If the old rivals finish top of their groups, they wouldn't be able to meet before Sunday's final.
That is a thrilling proposition given the final would decide not only the winner of this season's Tour Finals but also the holder of first place in the year-end world rankings.
Murray is currently in pole position after ending Djokovic's 122-week reign at the top, but the world No 2 will regain first place if he wins the Tour Finals for a record-equalling sixth time.
"It could come down to a match between me and Novak. Who knows what's going to happen the next few days," Murray said.
"For me and I'm sure for Novak, both of our goals would be to try to win the event.
"For him, whether that's by beating me, someone else, or for me if it's winning against Novak or another player, it doesn't change for us as players.
"But I think for the tournament, for everyone interested in tennis, that would probably be the perfect way to finish the year."