Gonzalez, the second seed from Chile, cruised past Spaniard Albert Montanes, 6-4, 6-4 to advance to a meeting with Martin. On Tuesday, the 22-year-old Gonzalez beat Croatian Zeljko Krajan before rain suspended play.
"I am very happy with the way I played, and I'm just trying to take advantage of my momentum," Gonzalez said. "I always had the match under control. Montanes is a very difficult player, but I put a lot of pressure on him because I was serving very well today."
Gonzalez won his first career title in February at the Vina del Mar in his native country.
Martin, the seventh seed from Spain, posted a 6-1, 7-5 victory over Argentine Franco Squillari, who lost in the 1998 final here. Martin has won all five meetings with Squillari.
"I'm here with my brother as my coach, and this confirms I'm in good shape," Martin said. "I played well last week in the challenger and I had to be good to beat Squillari today."
Top-seeded Chilean Marcelo Rios, who received a wild card, had little trouble in a 6-2, 6-4 victory over lucky loser Ruben Ramirez Hidalgo of Spain and will face Atillia Savolt of Hungary. Savolt beat German qualifier Oliver Gross, 7-5, 0-6, 7-5, in a match that began before Tuesday's rain.
Sixth seed David Sanchez of Spain joined Rios in the second round. Sanchez had a 6-2, 2-0 lead when Frenchman Richard Gasquet retired due to a viral infection.
Luis Horna of Peru defeated German qualifier Marcello Craca, 6-4, 4-6, 6-1, in another first-round match that began Tuesday.
Elsewhere, Sargis Sargsian of Armenia ousted Italian qualifier Filippo Volandri, 4-6, 7-6 (7-5), 6-1; Fernando Meligeni of Brazil posted a 6-2, 5-7, 6-2 win over Bohdan Ulihrach of the Czech Republic; and Costa Rican qualifier Juan Antonio Marin defeated Italian Stefano Galvani, 7-6 (7-4), 6-4.