Trump rejects campaign allies and political figures with pick; nomination expected to face bipartisan resistance in Senate.

President-elect Donald Trump has named Exxon Mobil Corp. Chief Executive Rex Tillerson as his secretary of state, a transition official said Monday, picking a veteran CEO who has had extensive overseas business dealings but whose relationships with foreign leaders could complicate his confirmation prospects. Mr. Tillerson was a comparatively late entry in the secretary of state competition, but he impressed the president-elect as a successful deal-maker in what one transition aide called the “Trumpian” mold. If confirmed by the U.S. Senate, Mr. Tillerson will be the public face of a diplomatic approach that envisions more cooperation with Russia and concessions from China on trade and security matters.

“His tenacity, broad experience and deep understanding of geopolitics make him an excellent choice for Secretary of State,” Mr. Trump said in a statement. “He will promote regional stability and focus on the core national security interests of the United States. Rex knows how to manage a global enterprise, which is crucial to running a successful State Department, and his relationships with leaders all over the world are second to none.

In choosing Mr. Tillerson, the president-elect passed over various campaign allies and established political figures. Among those he considered—and rejected—were former New York City Mayor Rudy Giuliani, one of his closest campaign advisers; U.S. Sen. Bob Corker (R., Tenn.), chairman of the Senate Foreign Relations Committee; and David Petraeus, a former director of the CIA.

Mr. Tillerson’s nomination faces bipartisan resistance in the Senate over his ties to Russian President Vladimir Putin. His company has long done business in Russia. He has known Mr. Putin since he represented Exxon’s interests in Russia during the regime of Boris Yeltsin. In a sign of the close relationship, the Kremlin bestowed the country’s Order of Friendship decoration on Mr. Tillerson after he struck a 2011 deal that gave Exxon access to prized Arctic resources and allowed Russian state oil company OAO Rosneft to invest in Exxon concessions around the world. Mr. Tillerson’s past opposition to sanctions on Russia is likely to trigger blowback among Senate Republicans, many of whom have rejected Mr. Trump’s more conciliatory stance toward the country and its president. No Senate Republicans have yet said they would vote against Mr. Tillerson. But a number of senators expressed reservations. Sen. Marco Rubio (R., Fla.), a member of the Foreign Relations Committee, the panel that would hold confirmation hearings on the nomination, said in a tweet Sunday that “being a ‘friend of Vladimir’ is not an attribute I am hoping for” in the next secretary of state.

A Trump administration will quickly have to contend with a volatile Middle East. Military involvement by Russia and Iran to boost the Assad regime in Syria has complicated the fight against Islamic State. The next secretary of state would be at the forefront of any negotiations with Russia on a resolution to the Syrian conflict while also tending to U.S. allies in the region who oppose the Assad regime. Mr. Trump’s approach to U.S. relations with Russia will be one of his most closely watched moves, given his comments about Russian President Vladimir Putin and U.S. intelligence assessment that Moscow used cyberattacks to try to help Mr. Trump in the election. Republican leaders in Congress recently have expressed deep misgivings about any warming to Mr. Putin.

“I am honored by President-elect Trump’s nomination and share his vision for restoring the credibility of the United States’ foreign relations and advancing our country’s national security,” Mr. Tillerson said in a statement. “We must focus on strengthening our alliances, pursuing shared national interests and enhancing the strength, security and sovereignty of the United States.”

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