Pena will portray the iconic activist, who was known for campaigning around the American labour movement and Latino civil rights during the 1960s and 1970s, reports Variety.
Ugly Betty's America Ferrera will star as Chavez's wife Helen, while Rosario Dawson will play Dolores Huerta, who was Chavez's partner in activism and co-founder of United Farm Workers.
The film is being developed by actors Diego Luna and Gael García Bernal, along with producer Pablo Cruz.
Written by Hotel Rwanda's Keir Pearson, the biopic will be directed by Luna, who made his directorial debut with Abel in 2010.
Luna explained: "This man inspired an entire community to see themselves as deserving of basic rights and to rise up against injustice.
"The film will send the message that change is in our hands - Chávez did something everyone thought impossible with a fearless grace that magnetized an entire country."
Pena can be seen next in the crime drama End of Watch opposite Jake Gyllenhaal, Anna Kendrick and Ferrera.
End of Watch is released on September 28, 2012 in the US. Details of a UK release are to be confirmed.
Watch the trailer for Crash below: