Kothari replaces SAIL chief C S Verma, who held the additional charge of CMD NMDC.
Earlier, the Appointments Committee of the Cabinet (ACC) has chosen Narendra Kothari, CEO of SAIL's Burnpur plant for the post of NMDC's CMD.
NMDC, the country's largest iron ore miner, had been without a full-time chairman after retirement of its regular head Rana Som on December 31, 2011.
"The Government of India has appointed Shri Narendra Kothari, CEO, SAIL as CMD on the Board of NMDC for a period of five years with effect from the date of assumption of charge of the post or till the date of his superannuation or until further orders, whichever is earlier," NMDC said in a filing to the BSE.
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It added that consequent to the development, Verma ceases to be CMD and Director of the Company with effect from April 21, 2014.
The Public Enterprises Selection Board (PESB) had in July 2011 suggested the name of M S Rana, CMD, Security Printing and Minting Corporation of India, for the post.
But, the Steel Ministry was not in concurrence with the PESB's recommendation and instead gave company's Technical Director N K Nanda additional charge.
Following some issues that cropped up, SAIL Chief C S Verma was given the additional task and he continued at the helm of affairs of the country's top iron ore producer.
NMDC produced 30.18 million tonnes (MT) iron ore in last fiscal and sold 30.50 MT of the key steel-making raw material.
The shares of the company closed at Rs 150.70 apiece, up 1.21 per cent on the BSE.