A spokesperson for the Department of Justice said Sessions believes "it is important for the American people to hear the truth directly from him."
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Sources said the Attorney General sent a letter over the weekend offering to testify.
The Chairman of the Senate Select Committee on Intelligence announced Monday the hearing will be held in open session Tuesday at 2:30 p.m.
Sessions is expected to take questions from senators about meetings with the Russian Ambassador and about his involvement in the firing of former FBI Director James Comey.
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The Associated Press contributed to this report.
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