It comes after the Basque Nationalist Party made a decision to remove its support for Rajoy after dozens of people linked to his ruling People's Party were jailed in a long-running corruption trial.
Bar any change, Rajoy will become the first Spanish premier to lose a no-confidence vote. It then released a series of private messages between Rajoy and Barcenas.
"Your isolation, Mr. Rajoy, is the epitaph of a political period, yours, which is over", the 46-year-old former economics professor said in parliament.
"In light of what we all know, I presume that the vote of no confidence will go ahead, and Pedro Sánchez will become the prime minister and I want to be the first to congratulate him", Rojoy told Parliament.
Rajoy became Spain's first sitting prime minister to give evidence in a trial when he was called as a witness a year ago, prompting calls for him to resign.
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In its ruling, the court said the credibility of Rajoy's testimony "should be questioned".
In a bid to secure the PNV's support, Sanchez vowed to stick to Rajoy's 2018 budget, which included concessions to the Basque Country and an increase in pensions demanded by the tiny party.
Last week's court ruling looked at the kickbacks-for-contracts scheme in place between 1999 and 2005, when Rajoy was a party member.
The Socialist Party's Pedro Sanchez, who is set to take over, had urged Rajoy to resign, saying his government was part of a chapter "the country is about to close".
Mr Rajoy responded that he had personally done nothing wrong, and warned the assembled politicians about backing a "Frankenstein government", in reference to the socialists needing support from the Left-wing Podemos, pro-independence Catalan parties and the Basque Nationalist Party (PNV), among others, to reach a majority. It is instead seeking a new general election, which could be won by their leader, Albert Rivera, according to recent polls. Rivera would have a strong chance of placing first in an election, but without winning a majority to form a government on its own.