Baros will have a medical on Tuesday with a view to signing a four-year contract, Villa said on their official website on Monday.
"We have reached an agreement with Liverpool to sign the player and the next step is for him to have a medical," said Villa operations director Steve Stride.
"Hopefully we can conclude the deal."
Baros, who is under contract with the European champions until 2007, joined Liverpool from Banik Ostrava for a fee of 3.6 million pounds in December 2001.
The 23-year-old Baros has scored 18 goals in 27 appearances for the Czech Republic.