The government is selling 41.22 crore shares, or 5 per cent, in NTPC at a floor or minimum price of Rs 122 apiece. If fully subscribed, the stake sale would fetch Rs 5,030 crore to the exchequer.
In the secondary market, the scrip was trading at Rs 124.80, down 1.62 per cent over its previous close.
The share sale is the first under Sebi's revised offer for sale (OFS) rules that allow the bidding for shares spread over two days.
While the issue opened for institutional bidders today, the retails investors, for whom 20 per cent shares have been reserved, will get to bid on Wednesday.
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Of the over 32.98 crore shares on offer for institutional investors, bids for over 2.10 crore shares have come in the initial hour of trade.
NTPC is the first company to hit the markets under the revised OFS guidelines of markets regulator Sebi.
The bidding would continue till 1530 hours on both the days.
SBICAP Securities, ICICI Securities, Edelweiss Securities and Deutsche Equities are the merchant bankers for the share sale.
The Cabinet in May had approved the 5 per cent stake sale in NTPC. The government holds 74.96 per cent in the firm. It had last sold stake in NTPC in February 2013.
NTPC would be the sixth PSU to hit markets in the current fiscal. The disinvestment department has held roadshows in Singapore, Hong Kong, London and in the US.
Volatile market conditions have affected the government's disinvestment plan, which mostly have commodity and oil stocks in the pipeline.