Twenty-three members have signed a Commons motion calling for the prime minister to be thrown from office.
They say he misled Parliament over the case for invading Iraq and want a probe by MPs to examine his conduct in relation to the war.
But the impeachment bid is widely expected to fail and probably will not even be debated in the Commons.
Downing Street says Tony Blair has already been cleared by four separate inquiries into the pre-war intelligence on Iraq.
The last attempted impeachment was of Foreign Secretary Lord Palmerston back in 1848.
Of the MPs 10 are Conservatives including Boris Johnson and former ministers John Gummer and Douglas Hogg.
MPs from Plaid Cymru, the SNP and the Lib Dems have also signed the motion.
The allegation against the prime minister is that in making the case against Iraq he was guilty of a serious breach of constitutional principles.
It says he has destroyed "the fundamental principle of parliamentary democracy" and wants a committee to decide whether there are grounds to impeach him on misconduct charges.
Plaid Cymru's Adam Price, who started the campaign, also wants a Commons debate on Mr Blair's conduct.
"We must make a stand or watch the democracy we have fought so often for against foreign enemies be subverted from within," he said.
"The rules of constitutional conduct had been brushed aside.
"People say politicians do nothing and are all alike but today we make a stand for parliamentary democracy," he added.