Former vice president Hamid Ansari and BJP national secretary Ram Lal were among those who queued up outside the Nirman Bhavan polling station in the first hour of voting.
Chief Minister and AAP national convener Arvind Kejriwal, who is eyeing to repeat his party's 2015 assembly performance, voted at the Rajpura Transport Authority polling station in the Civil Lines area.
Kejriwal, who is contesting the polls from the New Delhi seat, was accompanied by his wife Sunita and son Pulkit. Before leaving for voting, he sought his parents blessings.
President Ram Nath Kovind, former prime minister Manmohan Singh, West Delhi MP Parvesh Verma and Delhi BJP chief Manoj Tiwari have voted.
Minutes before polling began, Kejriwal tweeted, "Please go to cast vote. A special appeal to all the women - As your shoulder the responsibility at home, likewise, the responsibility of the country and Delhi is on your shoulders."
Union Home Minister Amit Shah, who led a very aggressive campaign and covered 60 assembly seats, appealed to voters to "free" the national capital from lies and votebank politics.
"By giving Delhi clean air, clean drinking water and every poor house, only the best capital of the world can make it a government with far-sighted thinking and strong intentions.
"I appeal to the people of Delhi to vote to free Delhi from lies and vote bank politics," Shah tweeted.
BJP president J P Nadda also appealed to all the voters to vote in large numbers.
"Each vote of you is important for the unity and integrity of the country and holistic development of Delhi. Your vote only will be script the golden future of Delhi. 'Pehle Matdan, Phir Jalpan'. Jai Hind," Nadda tweeted.
Polling began at 8 am and will end at 6 pm, an official said.
The minimum temperature in the city on Saturday settled at 7 degrees Celsius, three notches below the season's normal.
Shallow fog engulfed some parts of the national capital, leading to 'very poor' air quality, a MeT official said.
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