The result is also being billed as a pointer to the outcome of the general election later this year, with analysts saying that disillusioned voters seeking change will play a key role in both votes.
After nearly eight years in power, the centrist Civic Platform (PO) -- associated with Komorowski -- is running neck and neck in the polls with Duda's right-wing opposition Law and Justice Party (PiS).
Komorowski, a 62-year-old communist-era dissident who was jailed by the regime, was stunned by his razor-thin defeat in the first round to his energetic challenger on May 10.
"I voted for Duda because I want change," public sector employee Wieslawa Lorenc, 46, told AFP after casting her ballot Sunday in the Warsaw suburb of Mokotow.
"The retirement age just isn't right. Miners, nurses, teachers, they're not earning enough and the job market is bad."
Head of state since 2010, Komorowski is a seasoned defence specialist who garnered support from the Polish-born former US national security advisor Zbigniew Brzezinski as well as a bevy of Polish actors and athletes.
"With a very heavy heart, I voted for Komorowski," Warsaw voter Alicja, 34, told AFP.
She had backed anti-establishment candidate, rock star Pawel Kukiz, in round one to protest the "lack of opportunity for young people on the job market."
Analysts insist that Sunday's vote is too close to call.
"The victory of one or the other will be a narrow one and is impossible to predict on the basis of polls," Stanislaw Mocek, a political scientist at the Polish Academy of Sciences told AFP.
The Polish head of state acts as commander in chief of the armed forces, heads foreign policy and is able to introduce and veto legislation.
In power since 2007, the party is seen as having failed to keep its promises in key areas like administrative and tax reform.
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