Mr Blair will see the Queen and leave office after his final prime minister's questions session in the Commons and saying farewell to Downing St staff.
Mr Brown is then expected to travel to meet the Queen, who will formally offer him the role in the early afternoon.
Mr Brown is expected to begin his Cabinet reshuffle by naming the next chancellor and home secretary.
Priorities
Trade and Industry Secretary Alistair Darling, a close ally of Mr Brown, is widely tipped to become chancellor.
John Reid has also said he will step down as home secretary, leaving another Cabinet seat empty.
A fuller reshuffle of government jobs is expected on Thursday.
Mr Brown, who has been chancellor since Mr Blair became prime minister in 1997, has promised to create a government "of all the talents".
He has already offered former Liberal Democrat leader Lord Ashdown the job of Northern Ireland secretary, but this was turned down.
Mr Brown has singled out education and affordable housing as two of his key concerns, but says the NHS is his "immediate priority".
Iraq 'lessons'
He has also admitted that Iraq is "a divisive issue for our party and our country" and pledged to "learn lessons that need to be learned".
The parents of soldiers who have died in Iraq will protest in Downing Street as Mr Blair leaves No 10.
Members of Military Families Against the War say they are determined the outgoing PM "will not be allowed to forget the suffering he has caused".
The mechanics of leaving office, means Mr Blair is expected to have his final prime minister's questions in the Commons, then travel to Downing Street to say farewell to staff before heading to Buckingham Palace to see the Queen and resign.
Mr Brown will then be asked to the Palace where in a meeting with the Queen he will formally become prime minister.
Once he leaves office, Mr Blair is expected to travel north to attend a meeting in his Sedgefield constituency, in the north east of England, on Wednesday evening to announce he is standing down as an MP after 24 years.
It is thought the decision to step down as a Member of Parliament after 24 years depends on him being confirmed by the Middle East "quartet" of the US, Russia, the UN and the EU as an envoy to the region.
John Prescott will step down from frontline politics after 10 years as deputy prime minister. It is not certain whether Mr Brown will appoint a replacement.
http://news.bbc.co.uk/go/pr/fr/-/2/hi/uk_news/politics/6243558.stm
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