The winning numbers were 26, 27, 46, 47, 52 and 58. The bonus number was 48.
The jackpot comes after 14 consecutive rollovers found no winner, the BBC reported.
British TV presenter Noel Edmonds pushed the button for the lottery draw, more than two decades after presenting the first National Lottery show in November 1994, the report said.
Even though Saturday's prize total is to be shared, if each ticket is held by an individual, their 33 million pounds prize would make them the joint biggest National Lottery winners.
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The company said it had expected to sell at least 400 tickets per second online and in shops in the hours before sales stopped last night.
New rules meant the jackpot was guaranteed to be won, even if no-one picked all six numbers, as those who match five and the bonus ball were next in line for the top prize.
The new rules guaranteeing there would be a payout were brought in for the first draw after a jackpot reaches 50 million pounds.
The previous largest National Lottery jackpot was 42 million pounds, which was shared between three separate ticket holders in January 1996.
However, Saturday's prize is still dwarfed by the the biggest UK win in the Euromillions lottery, a draw where prize money comes from tickets sales in several European countries.
Colin and Chris Weir from North Ayrshire collected 161.6 million pounds in 2011.