The two main parties both claim they want a fresh power-sharing government installed as soon as possible, but the enmity between them seems entrenched, with neither side prepared to give ground.
Snap elections were called in January after long-simmering tensions boiled over between Catholic, Irish Republican socialists Sinn Fein and the Democratic Unionist Party, which is Protestant, conservative and pro-British in its outlook.
"I'd be more pessimistic than optimistic that the DUP and Sinn Fein can get back in a government together quickly," Jonathan Tonge, a Northern Ireland politics expert at Liverpool University, told AFP in a view echoed widely by analysts.
Sinn Fein's deputy first minister Martin McGuinness quit in January, saying he could no longer work with Northern Ireland's first minister Arlene Foster, the DUP leader.
McGuinness resigned in protest over a botched green heating scheme, the breaking point after months of tensions with the DUP.
Foster had instigated the scheme when she was the province's economy minister.
'Disrespect and contempt'
McGuinness is not standing again due to ill health but his successor as Sinn Fein's leader in Northern Ireland, Michelle O'Neill, is showing no sign of softening the rhetoric.
"People are angry at the arrogance, disrespect and contempt," she told Foster on Tuesday in a feisty televised debate.
Gerry Kelly, a Sinn Fein north Belfast candidate, told AFP his party had taken a "huge decision".
"We could have sat on our seats for four of five years, but there were issues that were big enough as far as we're concerned to bring back to the public," he said.
Throughout the election campaign, Foster has appealed for unionists to resist Sinn Fein's demands.
"If you feed a crocodile it will keep coming back for more," she told a party rally.
If the DUP and Sinn Fein end up as the two biggest parties -- as polls predict -- and cannot agree to form a power-sharing executive within three weeks, the governance of Northern Ireland will probably revert from Belfast to London for the foreseeable future.
Aside from handing over budget control, business groups are concerned that would hinder Northern Ireland's ability to attract much-needed international investment and tourism.
Brexit a 'hostile action'
Voters head to the polls against the backdrop of Brexit, prompting uncertainty over the province's future relationship with the Republic of Ireland.
Sinn Fein leader Gerry Adams in January described Brexit as a "hostile action" by the British government, which will affect the border and have a "negative impact" on the province's peace agreement.
In last June's referendum on EU membership, Northern Ireland voted to remain in the bloc but was outvoted by an overall British majority of 52 percent to leave.
Ahead of divorce talks starting, Brussels and Britain have emphasised the importance of the 1998 Good Friday Agreement -- which ended three decades of violence and saw the checkpoints of the border replaced with an open frontier.
Both have rejected the idea of imposing a hard border after Britain leaves the bloc, but with Prime Minister Theresa May vowing to end free movement of EU nationals it is unclear how this will be possible in practical terms.
Britain's Northern Ireland minister James Brokenshire travelled to Brussels on Wednesday, where he said his government "will take no risks" with political stability in the province.
Elections in Northern Ireland usually see voters make their choice along tribal lines between unionists and nationalists.
Tonge argues that the "sectarian dynamics" in elections will ensure business as usual, regardless of unionist disquiet over the DUP's handling of the costly bungled energy scheme.
"If you ask an ordinary unionist voter, 'would you rather pay £50 to £100 a year to pay for this heating scandal or would you have a Sinn Fein first minister?', they take the financial hit," he said.
The polls are due to open at 7:00am (0700 GMT) and close at 10:00pm.
Northern Ireland's remotest polling station got its ballot box on Wednesday after a choppy ferry journey to the 140 residents on Rathlin Island.
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