High percentage polls are expected in many areas, particularly the Western Cape, where half the province's 2.2-million registered voters had already visited the polls by mid-afternoon.
In Gauteng, around 3.9-million voters had cast their ballots by 5pm, out of some 4.9-million registered voters.
One of the more serious incidents occurred in Botshabelo in the Free State, when four Democratic Alliance members were arrested and then released on bail of R100 each after being detained in cells for four hours.
Advocate Pieter Geldenhuys, responsible for organising their release, said he had to drive to Botshabelo before police would release the men.
DA MPL Darryl Worth and three other DA members allegedly drove into a voting station in a vehicle bearing a DA logo.
"Seventeen police officers and five cars surrounded the members in an American-style arrest. This is a complete over-reaction and an abuse of state power," said DA spokesman Andries Botha.
Election rules dictate that no electioneering may take place at a voting station.
Other hiccups included several incidents around the country of parties accusing each other of electoral misconduct.
These included the IFP claiming "ANC activists" were seen pasting voter registration stickers into the identity documents of voters in KwaZulu-Natal.
The ANC denied the claims, but according to the Independent Electoral Commission (IEC), police are investigating.
IEC chief electoral officer Pansy Tlakula and IEC chairwoman Brigalia Bam both welcomed voters' enthusiasm.
Tlakula said the IEC expected voting to be completed smoothly when polls closed at 9pm: "The IEC learnt a lot from the 1994 and 1999 elections".
Another minor hiccup was a spat between Inkatha Freedom Party leader Mangosuthu Buthelezi and Defence Minister Mosiuoa Lekota.
Buthelezi had been due to vote at 8am at the Buthelezi Tribal Court voting station, but postponed when he heard Lekota had arrived there unexpectedly to check on security and levels of stability.
The DA also accused the ANC of trying to use the state to discredit the DA on election day, after the ANC laid charges under the Identification Act against persons accused of "defacing" identity documents with DA stickers.
Most of the country's political leaders used the earliest opportunity to cast their ballots, with President Thabo Mbeki leading the way at Colbyn polling station in Pretoria just after 7am, amid jokes that he was sporting an afro hairstyle in his ID photo.
He said the big day had come and it was now time for the politicians, who had done all the talking to stop.
"It's now time for the people to speak," he said.
At the Transvaal Automobile Club in Houghton, Johannesburg, South Africa's favourite pensioner, former president Nelson Mandela, arrived supported by his aide Zelda la Grange.
He joked that he would have dressed smartly if he had known there would be so many journalists.
Asked how it felt to be able to vote for only the third time in his life, the 85-year-old said: "I feel elated as I am able to vote again."
Another former president, F W de Klerk, visited the voting station at Sonstraal Primary School near Paarl to make his mark.
He told journalists afterwards he did not expect any major surprises in the election, but he anticipated Patricia de Lille's Independent Democrats might make an impact on the opposition vote.
"I supported my old party -- the New National Party," he said.
DA leader Tony Leon joked and smiled his way to the front of the queue at Johannesburg's Saxonwold Primary School.
"I feel fine. I feel strong. It's in the hands of the voting people now," said Leon, who is hoping that his party will get up to 20 percent of the vote.
New National Party leader Marthinus van Schalkwyk arrived with his wife Suzette to vote at the Jan van Riebeeck High School in Cape Town.
Side effects to the election included a bottle store owner in Brakpan who was pleased the nearby polling station had given his business a significant boost.
"Sales are much better than a normal Wednesday and a bit better than any other public holiday," said Joao Achadinha, owner of Sherwood Liquors. "I actually wouldn't mind if they had an election more often. This is great." - Sapa.
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