56-year-old Srivastava succeeded Deepak Mohan Spolia who had been made Chief Secretary in December 2012.
Srivastava, a 1980-batch IAS officer of Union Territory cadre, was working as Special Secretary and Financial Adviser in the Ministry of Health and Family Welfare.
Earlier this month, Chief Minister Arvind Kejriwal had sent a letter to the Union Home Ministry requesting it to appoint Srivastava as new Chief Secretary.
His previous postings include Vice Chairman of Delhi Development Authority (DDA) and Chief Secretary of Goa.
Spolia, a 1979-batch IAS officer, has been transferred as Financial Commissioner.
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