Pillai succeeds B Muthuraman, who retires today after 48 years of association with the Tata group.
The new chairman's appointment is with effect from September 26, 2014, Tata International Ltd (TIL) said in a statement.
Before becoming Home Secretary, Pillai also held the posts of Commerce Secretary and Secretary of the Department of Justice in the Ministry of Law & Justice.
As Special Secretary in the Commerce Ministry, he was India's Chief negotiator at the WTO.
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He is also Chairman of IvyCap Ventures and serves on the boards of several companies, including Hindustan Petroleum Corporation Ltd and the Data Security Council of India.
Established in 1962, TIL's key business verticals are leather and leather products, metals trading, minerals trading, distribution (auto and allied) and agri trading with a presence in manufacturing and supply chain integration in select businesses.
It has presence in 40 countries, spanning Africa, Europe, Middle East, Latin America and Asia and has spearheaded forays into new geographies for the group. It had a turnover of USD 1.7 billion in 2013-14 and employs about 10,000 people.