Thousands of voters queued up to cast their votes at the polling stations that opened at 8:00 a.m. (local time).
Over 15 million voters are expected to exercise their franchise to decide the fate of over 1,600 candidates, including five of Indian-origin, contesting from over 55 political parities.
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In the 150-seat House of Representatives, Labor currently holds 55 seats, the coalition 90 and five seats are held by minor parties or independents.
The main contest is between Turnbull and his conservative coalition against a Labor opposition led by Shorten.
A Newspoll published in The Australian showed Turnbull's Liberal/National coalition 50.5 to 49.5% in front on a two-party basis.
The UK's decision to leave the European Union appears to have benefited Turnbull.
Australian Election Commission said it had 75,000 people working around the country in about 7000 polling stations.
Meanwhile, four men were reportedly arrested overnight and later released for allegedly damaging polling booths in St Kilda area in Melbourne.
Victoria police said a number of people had damaged signs and posters at polling booths in the area and elsewhere.
In Sydney, 61-year-old Turnbull voted along with his wife Lucy at the Double Bay Public Schoolin his seat of Wentworth.
He repeated his call for voters to choose the Coalition and avoid a hung parliament.
"As I said there's never been a more exciting time to vote for a stable majority Coalition government, an economic plan that secures our future," he said.
Shorten, 49, continued his last minute campaign in the key marginal seats of Reid, Lindsay and Macquariein western Sydney. He is expected tofly to Melbourne this afternoon to cast his vote in his electorate of Maribyrnong.
Shorten said he was confident Labor could win.
"Labor is very competitive," he said, adding"I know that some of the conservative political papers have run their drum beat and whatever happens, the Liberals will win. The fact of the matter is that Labor's agenda has been speaking to the daily lives and experiences of Australians."
In May, Turnbull announced double dissolution of Parliament which led to two months of election campaign filled with slogans and promises.
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