The Polish world No. 12 was stunned 5-7, 6-3, 3-6 by the 143rd-ranked British player, who picked up the biggest win of his career and progressed to the next round in brilliant fashion.
Hurkacz, meanwhile, was sent packing from the Tokyo 2020 Games, Polish broadcaster TVP Sport reported.
The 24-year-old was the last Pole still standing in the singles at the Olympic tournament in Japan.
A day earlier, Poland's Iga Świątek crashed out of the women's singles in Tokyo, after being eliminated by Paula Badosa of Spain in the second round.
Świątek, the 2020 French Open champion who turned 20 in May, is scheduled to play mixed doubles with countryman Łukasz Kubot at the Tokyo Olympics on Wednesday.
Team Poland is still waiting for its first medal at the Summer Olympics in Japan.
(gs)
Source: TVP Sport, Eurosport, PAP