The XXV Amendment of the United States Constitution, Section 1 (Ratified February 10, 1967) provides that, "In case of the removal of the President from office or of his death or resignation, the Vice President shall become President."
Hopefully, the XXV Amendment will never need to be instituted. The last time this Amendment was attempted to be used was in 1981, when President Ronald Reagan was wounded in an assassination attempt in Washington, D.C. Fortunately, President Reagan was at no time incapacitated to the extent that he could not continue his duties. But, the then Secretary of State, Alexander Haig, took it upon himself to declare himself the acting President, until such time as President Reagan, so he thought, was able to continue. I suppose Secretary Haig had not familiarized himself with the XXV Amendment, but should he had, he would have known he was fourth in line.
Clearly, in the event that the President cannot continue to serve, per the conditions set forth in Section 1, the first order of succession goes to the Vice President, which in Reagan's case, would have been George Bush.
Following the Vice President, the order of succession is as follows:
Speaker of the House of Representatives
President pro tempore of the Senate
Secretary of State
Secretary of the Treasury
Secretary of Defense
Secretary of the Interior
Secretary of Agriculture
Secretary of Commerce
Secretary of Labor
Secretary of Health and Human Services
Secretary of Housing and Urban Development
Secretary of Transportation
Secretary of Energy
Secretary of Education
Secretary of Veterans' Affairs
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