The tiny northeastern town in the middle of the forest, near the Canadian border, has traditionally voted "first in the nation" since 1960.
Neighboring village Millsfield also begins voting at midnight but a third village in the area, which typically follows the same tradition, canceled overnight voting due to the coronavirus pandemic.
Most polling stations on the East Coast will open at 6:00 or 7:00 am (1100 or 1200 GMT) on Tuesday.
While many early votes are believed to have been cast by Democrats -- encouraged by Biden to take advantage of the opportunity -- Trump's campaign is hoping for a massive wave of Republican supporters voting in person on Tuesday.
President Donald Trump on Tuesday predicted a "beautiful victory" hours before polls open in Nov. 3 presidential race.
"We're going to have another beautiful victory tomorrow," he said at a rally in Grand Rapids, Michigan late Monday.
"We're going to make history once again," he said.
Trump earlier rallied in Kenosha, Wisconsin, which was at the center of anti-racism protests this summer after African-American Jacob Blake was shot in the back by the police.
The US president was in a final hour bid to prove the polls wrong, while his Democratic challenger Joe Biden predicted victory and told America to "take back" democracy.
"We brought law and order to Kenosha," Trump said to cheers, as soon as he took the stage. "They're waging war on our police."
The US president is trailing Biden in almost every poll amid his poor handling of the COVID-19 pandemic that has taken some 231,000 American lives and badly damaged the economy that had been his biggest selling point.