Gernot Trauner - one of three changes - opened the scoring for his nation as early as the ninth minute, and although Krzysztof Piatek equalised before the half-hour mark, Poland simply could not withstand Austria's superior class in Berlin.
Christopher Baumgartner scored a delightful second after a clever dummy from Marko Arnautovic, another name brought into the team, and the national team's all-time leading goalscorer confirmed the three points from the penalty spot with 12 minutes remaining.
Austria now move onto three points, keeping them in the hunt for a top-two spot in Group D, while Poland must defeat France to have any chance of progressing through to the last 16.
Nothing to separate teams in lively first half
Both managers decided to ring the changes after their opening-match defeats, yet the big news was Robert Lewandowski only being deemed fit enough to take a place on the substitutes' bench despite recovering from a minor groin issue.
A combination of rain and smoke greeted the two nations as they made their way out at the Olympiastadion, Austria reacting better to the hostile atmosphere.
Ralf Rangnick's side had dominated and deserved their ninth-minute lead, Philipp Mwene getting down the left to deliver a cross for Trauner, who powered a header inside the near post.
While Austria remained a threat, Poland should have probably equalised before the end of the first quarter, Nicola Zalewski blazing the ball over the crossbar from 15 yards out having been picked out at the far side of the penalty area.
However, he was not made to rue that miss as Poland got back on level terms on the half hour. Austria's backline initially made blocks to keep their clean sheet intact, only for the ball to drop fortuitously for Piatek who kept his composure and fired home from close range.
With one of the last actions of the first half, Piotr Zielinski saw a well-struck free kick kept out by Austria goalkeeper Patrick Pentz, but going behind would have been somewhat harsh on Austria after what had been an even encounter.
Arnautovic inspires Austria to victory
Interestingly, both managers opted to make a change at the break, with Poland's alteration seeing Jakub Moder come on for Jakub Piotrowski and Austria's Patrick Wimmer replacing Florian Grillitsch.
Wimmer made an instant impact, providing the corner for Stefan Posch to get a header on target, but it was too close to Wojciech Szczesny to threaten a goal.
At the 60-minute mark, it was time for Lewandowski to make his overdue entrance to the tournament, along with Karol Swiderski, as Michal Probierz made a double change in attack.
Lewandowski's first contribution was receiving a harsh yellow for an elbow when contesting an aerial ball, and the Barcelona man then watched on helplessly as Austria went in front in some style.
Arnautovic smartly dummied a pass from the left in order for it to reach Baumgartner, who advanced towards the edge of the area under minimal pressure before unleashing a shot into the bottom corner from 16 yards.
Poland almost netted an immediate leveller through Swiderski, whose swerving effort was beaten away by Pentz, yet it was Austria who generally remained in the ascendancy, Szczesny making an outstanding stop down to his right to deny Wimmer.
Moments later, however, Austria had their third. After Marcel Sabitzer was brought down inside the area by Szczesny having got through on goal, Arnautovic converted the spot kick with aplomb for his 37th international goal.
Austria wasted further opportunities as the clock ticked down, Konrad Laimer most notably missing the target having rounded Szczesny, yet it mattered little as Rangnick's side extended their recent run to just two defeats in 18 matches.
Man of the Match
While Arnautovic did not necessarily have the greatest impact throughout the contest, it was his shrewdness that led to Baumgartner putting Austria back in front as the game entered the final quarter.
That took away some of the hope that Poland had when Lewandowski had been introduced, and Arnautovic ended all of it with a ruthless finish from the penalty spot.
When do Poland, Austria play again at Euro 2024?
Austria head into Tuesday's game with Netherlands knowing that they will almost certainly make the last 16 if they avoid defeat.
Meanwhile, Poland's only hope is overcoming France, who may still need to get something from that fixture.