Democrats are taking control of the US Congress after 12 years as a minority - with a woman at the helm of the House of Representatives for the first time.
Nancy Pelosi will become speaker in a ceremony at 1200 (1700 GMT), and will be the second in line to the presidency, after the vice-president.
In another first, a representative will use the Koran not Bible for their vow.
Correspondents say the shift in power could lead to challenges to the authority of the White House.
Unity appeal
Ms Pelosi, who will be referred to as "Madam Speaker", has vowed to clean-up Congress, saying: "It takes a woman to clean house" - a reference to the corruption seen as widespread on Capitol Hill.
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She is one of 86 women set to serve in this Congress - the highest number in US history - although the institution remains overwhelmingly male.
In the face of a Democratic majority in both the Senate and the House, Mr Bush, who has already held talks with Ms Pelosi, made an appeal for congressional unity.
We've all been entrusted with public office at a momentous time in our nation's history and together we have important things to do," Mr Bush said in a speech on Wednesday morning.
"It is time to set aside politics and focus on the future," he added, urging Democrats not to pass "bills that are simply political" statements.
Leading Democrats have also called for a new spirit of bi-partisanship in Washington.
Senator Charles Schumer said: "We certainly want to work with the president. We hope that when the president says compromise, it means more than do it my way, which is what he's meant in the past."
Ms Pelosi has published a manifesto for the Democrats' first 100 hours. Along with a promise to stamp out corruption, it includes plans to boost the minimum wage, increase stem cell research, and end subsidies for large oil companies.
Democrats have also said they will put pressure on Mr Bush to begin a phased withdrawal from Iraq.
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