But in the eastern city of Benghazi, cradle of last year's uprising and now seeking more autonomy from the interim government, protesters stormed polling stations and burned hundreds of ballot papers.
Libyans are choosing a 200-member assembly which will elect a prime minister and cabinet before laying the ground for full parliamentary elections next year under a new constitution.
Candidates with Islamic agendas dominate the field of more than 3700 hopefuls, suggesting Libya will be the next Arab Spring country – after Egypt and Tunisia – to see religious parties secure a grip on power.
In Benghazi, witnesses said protesters stormed a polling station just after voting started and publicly burned hundreds of ballot slips in a bid to undermine the election's credibility.
One local election commission worker said two other polling stations in Benghazi also had their ballots boxes looted.
At one polling station hit by the protests, a man was shot in the arm, said local election official Ismail Al-Mjbali. Blood from the attack stained the floor and the man had been taken to hospital, Mjbali said.
In the capital Tripoli, voting was smooth. A loud cry of "Allahu akbar" ("God is greatest") went up inside a polling station there as the first woman cast her vote in a converted school building abuzz with the chatter of queueing locals.
"I can't describe the feeling. We paid the price, I have two martyrs in my family. I am certain the future will be good, Libya will be successful," Zainab Masri, a 50-year-old teacher, said of her first experience of voting.
"I am a Libyan citizen in free Libya," said Mahmud Mohammed Al-Bizamti. "I came today to be able to vote in a democratic way. Today is like a wedding for us."
Many easterners, whose region is home to the bulk of Libya's oil sector, are angry that the east has been allotted only 60 seats in the assembly compared to 102 for the west.
On Friday, armed groups in the east shut off Libya's oil exports to press their demands for greater representation in the new national assembly. At least three major oil-exporting terminals were affected.
"The country will be in a state of paralysis because no-one in the government is listening to us," said Hamed al-Hassi, a former rebel who now heads the High Military Council of Cyrenaica, the name of the eastern region.
Port agents said the oil depot closures would last 48 hours but the government sent a team yesterday to negotiate a full reopening of a sector that provides most of Libya's revenues.
In the latest attack on election authorities in the east, a helicopter carrying voting material had to make an emergency landing near Benghazi on Friday after being struck by anti-aircraft fire. One person on board was killed.
"There is no security in this country," complained Emad El-Sayih, deputy head of the High National Election Commission.
Concerns exist elsewhere. In the southern area of Kufra in the Sahara desert, tribal clashes are so fierce that election observers are unable to visit, and some question whether the vote can proceed in certain areas there.
In Gaddafi's hometown of Sirte, a former fishing village on the southern rim of the Mediterranean sea, the mood before the polls was restrained, with some saying they would not vote.
"They should take care of us first – look at our homes," said Abed Mohammed, a resident of District Two neighbourhood which saw some of the heaviest fighting and where Gaddafi was believed to have hidden before being captured and killed.
While analysts say it is hard to predict the political make-up of the new assembly, parties and candidates professing an attachment to Islamic values are dominating the field and very few are running on an exclusively secular ticket.
The Justice and Construction offshoot of Libya's Muslim Brotherhood is tipped to do well, as is al-Watan, the party of former CIA detainee and Islamist insurgent Abdel Hakim Belhadj.
Polls closed at 8pm last night but meaningful partial results are not due until later today.
