World number eight Dimitrov, who is chasing one of the four remaining berths for next month's eight-man season ending tournament, beat flamboyant Italian Fabio Fognini 6-3 7-6(2).
The Bulgarian, who won the tournament in 2013, will face defending champion Del Potro in Sunday's final after the Argentine beat Fernando Verdasco 6-7(4) 6-4 7-6(1).
Del Potro, ranked 19th, struggled early against Verdasco before coming back from a set down to secure victory with a blazing display in the third set tiebreak.
Rafael Nadal, Roger Federer, Alexander Zverev and Dominic Thiem have already secure places in the London finale.
(Reporting by Philip O'Connor, editing by Pritha Sarkar)
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