Djokovic and Federer will meet in the final of the Cincinnati Masters after battling their way past Marin Cilic and David Goffin respectively.
The Serb is aiming to continue his resurgence having scooped the Wimbledon title last month, battering Kevin Anderson in the final.
Should Novak Djokovic get the better of Federer today, he will become the first player since Rod Laver to have won all nine Masters titles throughout his career.
And Rusedski thinks that honour will give the 31-year-old an added incentive to scoop the prize.
He told Sky Sports: “If he holds all nine Masters titles, the first man since Rod Laver, it will be an incredible achievement.
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“It sometimes feels at times he is under the shadow of Nadal and Roger Federer but at one time he held all four Grand Slam titles and was by far the best player in the world.
“He should be able to say ‘hey guys, you have not held all four Grand Slam titles at the same time or all nine Masters titles’.
“I think he is desperate to win here in Cincinnati to complete the Golden Masters.
“He is one of the greatest movers on a tennis court ever. He is an exceptional athlete.”
Djokovic has seemed temperamental at times in Cincinnati so far.
He smashed his racket during his quarter-final victory over Milos Raonic on Friday.
But Rusedski only has positive words for his actions.
He added: “I like to see that emotion.
“It gets the frustration out of his system. You have to let the negative energy out then go out there refreshed.
“I think he desperately wants to win this title. He has never won here after being in five finals.
“When you stepped on court against Novak Djokovic you always knew you was going to be second best.
“At Wimbledon he was like the old Novak and this week he is winning the long matches.
“He was by far the dominating force in men’s tennis so it is good to see him back.”