The 64-year-old was confirmed by the Senate in a 56-43 vote. He is expected to soon be sworn in as the top American diplomat and occupy the Foggy Bottom headquarters of the State Department.
The important position of Secretary of State had been lying vacant for nearly two weeks after Tillerson's predecessor John Kerry left the office on January 20 with the expiry of the term of Barack Obama as the US President. Obama was succeeded by Donald Trump on January 20.
"Mr Tillerson led a global enterprise with 75,000 employees, possesses deep relationships around the world, and understands the critical role of US leadership," said Senator Bob Corker, Chairman of the Senate Foreign Relations Committee.
Former President George W Bush, former Vice President Dick Cheney, former secretaries of state James A Baker and Condoleezza Rice, former Secretary of Defense Robert Gates, and former Senator Sam Nunn had endorsed Tillerson's nomination.
In remarks on the Senate floor, Democratic Senator Elizabeth Warren said Tillerson's "extensive and longstanding ties with Russia" meant that the US couldn't trust him to be a strong advocate for their interests.
"Not only is Rex a world-class business man who has worked with companies in countries all around the globe, but he is an accomplished leader and tough negotiator," said Senator Jim Inhofe.
Paula Caballero, global director, Climate Program, World Resources Institute said as Secretary of State, Tillerson must shift from looking after business interests to looking after the needs of all Americans. "This will require continuing America's strong leadership to addressing climate change, one of the greatest economic and national security threats of our time," he said.
"There have even been reports that this Administration is considering dropping sanctions against Russia. There is bipartisan opposition to that idea in Congress, which will conduct vigorous oversight of the State Department," he said.
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