As events unfolded, Peru's foreign ministry said a "Mexican government plane" had been granted permission for overflight.
Mexican foreign minister announced on Monday that Bolivia's ex-president Evo Morales,60, would be granted asylum as the South American nation faced continued violence.
"Several minutes ago I received a phone call from (former) president Evo Morales in which he responded to our offer and verbally and formally requested political asylum in our country," Foreign Minister Marcelo Ebrard said.
"The Mexican foreign ministry, after consulting Interior Minister Olga Sanchez Cordero, made the decision to grant him asylum... for humanitarian reasons," the Mexican foreign minister added.
Ebrard asserted that Morales's "life and physical integrity are at risk in Bolivia."
As events unfolded, Peru's foreign ministry said a "Mexican government plane" had been granted permission for overflight and to refuel and had departed for Bolivia at 6:30 pm (2330 MT).
As violence spread amid Morales exit, Bolivia's armed forces said it would conduct joint operations with the police to prevent violence.
Earlier, Bolivia's police chief in La Paz Colonel Jose Barrenechea had called on General Williams Kaliman to "intervene" saying the police had been "overrun" as thousands of pro-Morales supporters marched through the city even as Morales called on the opposition to "pacify the country".
"The military command of the armed forces has arranged for joint operations with the police to prevent bloodshed and fighting amongst the Bolivian family," General Williams Kaliman said in a televised address to the nation.
Morales had resigned amid controversy over election results and had called for another election even as Army commanders and the police asked Morales to step down. Morales resigned on November 10 in a televised address.
Meanwhile, Senator Jeanine Anez, 52, who is constitutionally in line to become the interim president pledged to call fresh elections. "We are going to call elections, an electoral process that reflects the will of all Bolivians," Anez said.