He was administered the oath of office and oath of secrecy by Lieutenant Governor Kiran Bedi at a function at Gandhi Statue on Beach Road in Puducherry.
The five ministers who took oath were A Namassivayam, Malladi Krishna Rao, M Candassamy, M O H F Shahjahan and R Kamalakannan.
Narayanasamy, for whom this is the first term as Chief Minister, is the second Congress leader after P Shanmugam to head a Ministry without being a member of the Assembly.
The Congress which has 15 MLAs in the 30-member House has formed the Ministry with the support of the two DMK MLAs.
Since there were three contenders for the chief minister's post -- former Chief Minister V Vaithilingam, party head in Puducherry A Namassivayam and Narayanasamy -- there was a delay in choosing the next chief minister. While Narayansamy has become the Chief Minister, Namassivayam will be second most powerful in the cabinet, while Vaithilingam is likely to be the Speaker at the Assembly.
AICC general secretaries Mukul Wasnik, Chinna Reddy, DMK Treasurer and Leader of Opposition in Tamil Nadu M.K. Stalin, Tamil Nadu Congress Committee president E V K S Elangovan, Thirukovilur MLA K Ponmudi and newly elected MLAs of the Congress were among those present at the ceremony.
Narayanasamy comes from a humble background. His father, Velu, was a toddy tapper in a small village, Thavalakkuppam, in the Union Territory of Puducherry.
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He joined the Congress in his late 20s, and his loyalty to the party and the Congress first family is well known.
Rajiv Gandhi nominated him as the Rajya Sabha MP from Puducherry. During the UPA I and II, he held a number of important posts including that of the Union Minister of State for the Prime Minister's Office, Personnel, Public Grievances & Pensions, and Public Affairs. He has been a member of many Parliamentary subcommittees, and goodwill delegations.
Meanwhile, the new Lieutenant Governor Kiran Bedi, a retired IPS officer and earlier BJP's Chief Minister candidate in Delhi has banned Use of siren in cars of VIPs, including the escort and pilot vehicles of the Lieutenant Governor, has been banned in Puducherry.
However, emergency services like ambulances and fire service vehicles, will be exempted from the restriction on the use of siren.
Bedi also directed that no special privilege will be accorded for cars of VIPs such as stopping of traffic, so that people's right to freedom of movement is not hindered in any manner. This includes Lieutenant Governor's.