Both nations went into the tie in Sydney unbeaten in Group D, winning previous clashes with Greece and Georgia, to make their showdown a winner-takes-all battle.
Poland’s world No 117 Kamil Majchrzak set up his team for victory with a gutsy 6-3, 7-6(7/3) victory against Federico Delbonis, who is ranked 73 places higher.
That left 2021 Miami Open champion Hurkacz needing to beat 13th-ranked Schwartzman, and he did so in style, racing to a 6-1, 6-4 victory in 81 minutes.
“So happy for Team Poland, we are in the semis and super proud of that achievement,” said Hurkacz, who sent down 12 aces and won 85% of his first-serve points.
“We are a great team, have great team spirit and support each other and I think the atmosphere that we bring helps us play better.”
It was another solid win for Hurkacz after a career-best 2021 garnered three ATP Tour titles, as he warms up for the Australian Open which begins on Jan 17.
Schwartzman had stunned world No 4 Stefanos Tsitsipas on Monday.
Majchrzak has been a more-than-competent second singles player, enjoying one of the best weeks of his career with three wins in a row.
“It was very connected with the emotions and with the big fight of Federico. It was a very difficult game from the beginning until the end,” he said.
“My ranking maybe is out of the top 100, but I feel like I belong in the top 100 and more, so I’m going for it now,” he added.
The Roberto Bautista Agut-led Spain, runners-up to Serbia at the inaugural tournament in 2020, could also make semifinals if they beat Dusan Lajovic’s Serbia in an evening Group A tie.
Only the top nation from each of the four groups progresses to the knockouts.
The winner between Daniil Medvedev’s defending champions Russia or the Matteo Berrettini-led Italy, last year’s finalists, will also make the semifinals when they meet tomorrow in Group B.
The outcome of Group C is more complicated with all four teams – Britain, Canada, Germany and the US – still in contention.
They also play tomorrow.
Norway and Chile were already out of the hunt, making their clash today about pride.
World No 8 Casper Ruud ensured he ended the tournament on a winning note by beating Chilean Cristian Garin 6-4, 6-1 after his teammate Viktor Durasovic lost in three sets to Alejandro Tabilo.