Fernando Morientes has agreed personal terms with Valencia and is expected to complete his switch from Liverpool on Tuesday, subject to a medical.
The clubs negotiated a move for an undisclosed fee on Thursday and the 30-year-old will sign a three-year deal with the option of a further year.
Morientes has been at Anfield for 16 months and managed to score just 12 goals in 61 games.
His lack of form saw him left out of Spain's squad for the World Cup.
Morientes moved to Liverpool from Real Madrid for £6.3m in 2005 after he had excelled while on loan at Monaco.
"Everybody at Liverpool would like to wish 'Nando' all the best with his new club in Spain," said a statement on the Liverpool website.
On Tuesday Morientes' agent Gines Carvajal said the striker would not return to Spain and would fulfil the remaining two years of his Liverpool contract.
Morientes made his first division debut with Albacete in 1993 and joined Real Zaragoza two years later where he went on to score 28 league goals in two seasons.
In 1997 Real Zaragoza sold him for £4.5m to Real Madrid.
The striker won three European Cups and two league titles with Real but the arrival of Ronaldo in 2002 limited his chances.
Morientes moved on loan to Monaco, helping the French club reach the Champions League final in 2004, before they were beaten 3-0 by Porto.
He returned to Real Madrid at the start of the 2004-2005 season, but the arrival of Michael Owen again pushed him down the striking pecking order at Real and in January 2005 he joined Liverpool.
Although Morientes will not be going to the World Cup he has an impressive strike rate for Spain, scoring 26 goals in 43 international appearances.