Midfielder Sebastian Szymański opened the scoring for Poland with a long-range shot eight minutes into the match at Hampden Park stadium in Glasgow.
Captain Robert Lewandowski put Poland 2-0 ahead from a penalty in the 44th minute.
Billy Gilmour narrowed the deficit for Scotland, scoring two minutes after halftime, while Scott McTominay equalised for the home team in the 76th.
Roma midfielder Nicola Zalewski put the score at 3-2 in Poland's favour seven minutes into stoppage time.
Nicola Zalewski in action against Scotland in Glasgow on Thursday night. Photo: PAP/Leszek Szymański
The hard-fought away win marked a strong start to Poland's Nations League campaign and a promising lead-up to the 2026 World Cup qualifiers, which begin in March next year.
Poland are ranked 28th worldwide by football's governing body FIFA, while Scotland are No. 48 in the FIFA table.
Manager Michał Probierz's men will take on Croatia in Osijek on Sunday in their next Nations League fixture.
The Poles have been drawn to play Scotland, Croatia and Portugal in the group stage of the 2024/2025 UEFA Nations League.
The four teams will play one another at home and away in Group 1 of the top League A from September to November.
The Nations League is UEFA’s newest national-team competition that is now in its fourth edition.
The European football governing body says the 2024/2025 edition of the competition has been expanded with a new knockout round to be played in March 2025.
The League A group winners and runners-up will participate in home-and-away quarterfinals, with the winners of these ties qualifying for the final tournament in June 2025, according to the uefa.com website.
Meanwhile, the fourth-placed teams in League A will be automatically relegated to League B.
The competition's semifinals will take place on June 4 and 5, 2025. The winners will advance to the final on June 8, while the two beaten semifinalists will contest the match for third place earlier the same day.
The Nations League is designed to enable teams to play against those that are similarly ranked, while reducing the number of meaningless friendlies, UEFA said.
Portugal won the first edition of the Nations League in 2019, while France won the 2020/2021 UEFA Nations League, and Spain triumphed in the 2022/2023 edition.
2024/2025 UEFA Nations League
League A
Group A1: Croatia, Portugal, Poland, Scotland
Group A2: Italy, Belgium, France, Israel
Group A3: Netherlands, Hungary, Germany, Bosnia and Herzegovina
Group A4: Spain, Denmark, Switzerland, Serbia
Poland in June suffered an early exit from the Euro 2024 tournament in Germany, after losing its first two group-stage matches against the Netherlands and Austria and drawing 1-1 with France in its final game.
Poland finished last in their Group D and failed to advance to the knockout stage of the continental championships, with just one point from three group-stage games.
Scotland and Croatia were also eliminated from the Euro 2024 tournament after the group stage. Portugal, meanwhile, were knocked out in the quarterfinals by France.
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Source: IAR, PAP, pzpn.pl, uefa.com/uefa.com