The Polish quartet of Piotr Zyla, Maciej Kot, Mietus and Kamil Stoch led at the halfway stage on their own hill and were seemingly on their way to victory with two jumps remaining.
However a poor second effort from Mietus followed by solid leaps from Jaka Hvala and Peter Prevc gave Slovenia, who also had Jurij Tepes and Robert Kranjec in their team, the win.
Slovenia had to make do with third behind Germany and Austria in the first of six team events on the World Cup circuit this season but beat Poland by almost ten points in Zakopane.
Zyla, Kot, Mietus and Stoch combined to give Poland a score of 505.4 after the first round of jumping, well ahead of the Slovenian quartet who produced 479.7.
Solid efforts from Zyla and Kot kept Poland in front halfway through the second round however a below-par jump from Mietus allowed Slovenia to seize control.
Mietus jumped 108m for a total of 82.8 points with Hvala putting Slovenia into the lead ahead of the final eight jumps with a cushion of just shy of 18 points after jumping 126m for 124.6.
And, despite a fine effort from Stoch last time out, he jumped 130m for 129.5 points, Prevc's effort of 123.5m and 120.9 was enough for Slovenia to remain in first place for the win.
Austria, without newly crowned Four Hills champion Gregor Schlierenzauer, took third with 931.1 points in total well ahead of the German quartet in fourth with 908.4.