Polling nationwide began at 0500 GMT across the country, with voters standing in long lines before daybreak including some first-time "born free" voters -- those born after Namibia gained independence from South Africa in 1990.
"It's a rich country with poor people, so I hope there is more balance," said 43-year-old Elias while waiting to cast his vote.
The ruling South West Africa People's Organisation - better known as SWAPO - was forged from the embers of the anti-colonial and anti-apartheid struggle and has won every election in the 24 years since Namibia's independence.
"SWAPO is going to win. There is no 'if', SWAPO is going to win," she said.
Stations are due to close at 1900 GMT after 14 hours of voting. Around 1.2 million Namibians are eligible to cast their ballots at nearly 4,000 electronic voting places across the vast desert nation.
Other African nations such as Kenya have run pilot or limited e-voting, but none have done so on this scale.
Voting began slowly as presiding officers rolled out the new electronic voting system.
"The younger people get it first time, but the older ones you have to explain a little," said presiding officer Hertha Erastus.
At other stations, independent observers noted significant delays and long queues when the machines malfunctioned.
Namibians will choose 96 members of the national assembly and one of nine presidential candidates.
Current Prime Minister Hage Geingob, the man almost certain to be named the next president when the final tally is in, cast his vote in the Windhoek township of Katutura.
"We have plans already, we are not a new party. We have plans that we are going to implement," said Geingob after casting his vote.
Opposition parties had launched an 11th-hour court challenge to stop the vote from going ahead, saying the use of India-made e-voting machines could facilitate vote rigging.
But the Windhoek High Court dismissed the application on Wednesday.
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