The 33-year-old, who played for Mexico at the 2006 and 2010 World Cups after obtaining Mexican citizenship, said the time was right to make way for younger players.
"I consider my spell in the national team has reached its end, respecting the fact there is a good generation of youngsters coming up behind," Franco told Mexico's Acir radio on Thursday.
Franco, who won his 25th and last cap in Mexico's 3-1 loss to Argentina in the World Cup second round in South Africa in June, said he was looking at several options before deciding which club to join this season.
Mexico's interim coach Enrique Meza, who was in charge for the friendly 1-1 draw against world champions Spain last month, said he disagreed with picking naturalised players.
Efrain Flores, who has taken over from Meza as interim coach, overlooked Franco for Mexico's friendly at home to Ecuador on Saturday at the Omnilife stadium in Guadalajara.
The match will be the first for Ecuador's new coach, Colombian Reinaldo Rueda who took Honduras to the World Cup in South Africa.
Mexico, who meet Colombia in another friendly in Monterrey on Tuesday, will appoint a permanent coach at the end of the year to replace Javier Aguirre, who quit after the World Cup.
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