Thirteen contenders are in the race, including several backed by the country’s largest political parties.
Among the front-runners are centrist Warsaw Mayor Rafał Trzaskowski, representing the ruling Civic Coalition (KO), and right-wing opposition contender Karol Nawrocki, supported by the formerly governing Law and Justice (PiS) party.
Polling strongly in third place shortly before election day is far-right candidate Sławomir Mentzen of the Confederation party.
Trailing him in the polls are lower-house Speaker Szymon Hołownia, co-founder of the centre-right Third Way alliance; leftist senator Magdalena Biejat from the co-governing New Left group; and Adrian Zandberg from the left-wing opposition Together party.
The seven remaining candidates include controversial far-right politician Grzegorz Braun; left-wing veteran Joanna Senyszyn; right-wing Republican Marek Jakubiak; journalist Krzysztof Stanowski; economist Artur Bartoszewicz; lawyer Marek Woch; and pro-Russian figure Maciej Maciak.
The winner will serve a five-year term as head of state, overseeing defence and foreign policy and holding veto power over legislation.
Incumbent President Andrzej Duda, in office since 2015, is barred from seeking a third term under Poland's constitution. His second term ends on August 6.
If none of the candidates wins more than 50 percent the vote, a runoff election will be held on June 1.
Polling stations will open at 7 a.m. and close at 9 p.m. on Sunday.
A media blackout begins on Friday at midnight under which domestic news organisations are prohibited from publishing opinion polls showing the level of support for candidates.
The ban lasts until polling stations close. Political campaigning is also forbidden during this period.
More than half a million Poles living abroad have registered to vote by absentee ballot in the country's presidential election, Sylwester Marciniak, head of the National Electoral Commission, told reporters on Friday.
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Source: Polish Radio, IAR, PAP