More than 139,000 voting stations opened at 6 am local time across the country, with turnout expected to hit a record high.
Voters have been galvanised by anger over the sprawling bribery and abuse of power scandal that brought down Park, which catalysed frustrations over jobs and slowing growth.
Left-leaning Moon Jae-In, a former human rights lawyer, has held a commanding lead in opinion polls for months, with the final Gallup Korea survey before a week-long pre-election blackout giving him 38 percent support, followed by former tech mogul Ahn Cheol-Soo on 20 percent.
The campaign has focused largely on the economy, with North Korea less prominent, but after a decade of conservative rule a Moon victory could mean a sea change in Seoul's approach towards both Pyongyang and key ally Washington.
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The 64-year-old -- who is accused of being soft on the North by his critics -- has advocated dialogue to defuse tensions and to bring it to negotiations, and is seen to favour more independence in relations with the US, Seoul's security guarantor with 28,500 troops in the country.
The North has carried out two nuclear tests and a series of missile launches since the start of last year in its quest to develop a missile capable of delivering a nuclear warhead to the US mainland, and Washington has said military action was an option, sending fears of conflict spiralling.
More recently US President Donald Trump has softened his message, saying he would be "honoured" to meet the North's leader, Kim Jong-Un.
But for many South Korean voters, corruption, slowing growth, unemployment, and even air pollution from China top the list of concerns.
South Korea's rapid growth from the 1970s to 1990s pulled a war-ravaged nation out of poverty but slowed as the economy matured, and unemployment among under-30s is now at a record 10 percent.
Frustration over widening inequality in wealth and opportunities fuelled anger over Park's scandal, which exposed the cosy and corrupt ties between regulators and powerful family-oriented conglomerates, known as chaebols, that have endured for decades.