"New series of Rs 500 denomination notes (were) introduced today in New Delhi at SBI Parliament Street Branch," the Ministry of Finance said in a tweet.
Banks have been advised to make separate arrangements for the elderly and women, a senior government official told PTI.
Some branches like SBI Main branch in Delhi have started distribution of Rs 500 notes.
Only Rs 2,000 notes, apart from Rs 100 and below, have been available since Prime Minister Narendra Modi on Tuesday night announced the surprise decision to demonetise higher denomination notes.
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However, 500 and 2,000 rupee notes dispensed through ATMs will be possible after recalibration of such machines as these are of different sizes.
According to the central bank statement, the new Rs 500 banknotes bear signature of Reserve Bank of India Governor Urjit Patel.
The stone grey-coloured note bears year of printing '2016' and Swachh Bharat logo printed on the reverse.
The new Rs 500 note is different from the earlier in colour, size, theme, location of security features and design elements.
"The banknote also has features (intaglio printing of Mahatma Gandhi portrait, Ashoka Pillar emblem, bleed lines, circle with 500 in the right, and the identification mark) which enable the visually impaired person to identify the denomination," it said.