This is Novak’s fifth runner-up finish in Cincinnati, following his Final appearances in 2008-09 and 2011-12.
Novak stays on course in historic bid to become the first player to complete the Career Golden Masters with a 4-6, 7-6, 6-2 win over Dolgopolov.
Nole reached the last four at the Cincinnati Masters on Friday as he outplayed no.5 seed Stan Wawrinka 6-4, 6-1 in a rematch of the French Open final.
Nole overcame a test from David Goffin, securing a 6-4, 2-6, 6-3 victory in the Western & Southern Open third round on Thursday.
Novak beat world no.42 Benoit Paire 7-5, 6-2 on Wednesday to move into the Western & Southern Open last 16. He next faces David Goffin.
Novak will open campaign against no.42-ranked Frenchman Benoit Paire (LL, 0-0) on Wednesday.
Andy shattered Nole’s perfect record at Masters 1000 events in 2015, beating him 6-4, 4-6, 6-3 in the Rogers Cup final on Sunday.
Nole beat world no.49 Jeremy Chardy 6-4, 6-4 in 80 minutes to reach his fourth Rogers Cup final. He faces Andy Murray on Sunday.
Novak rallied from a set and a break down and saved two match points before going on to beat Ernests Gulbis 5-7, 7-6 (7), 6-1 in the Rogers Cup QF.
Novak beat world no.35 Jack Sock 6-2, 6-1 in just 54 minutes to move into the Rogers Cup quarter-finals.