A spokesperson for the Department of Justice said Sessions believes "it is important for the American people to hear the truth directly from him."
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.
The Associated Press contributed to this report.
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