The former Bolivian president has accepted political asylum in Mexico as violence in La Paz grows after his resignation.
Evo Morales resigned on Sunday after weeks of huge protests in Bolivia over a disputed presidential election.
However, the resignations of every constitutionally designated successor left unclear who will take his place and how.
Amid angry scenes in the capital, Mr Morales tweeted that he was leaving on Monday evening.
Mexico’s Foreign Relations Secretary Marcelo Ebrard confirmed in a tweet that the former leader was on a plane sent by Mexico City.
“I am leaving for Mexico, grateful for the openness of these brothers who offered us asylum to protect our life,” Mr Morales tweeted.
“It hurts me to leave the country, for political reasons, but I will always be concerned. I will return soon, with more strength and energy.”
Angry supporters of the socialist leader set barricades ablaze to block some roads leading to the country’s main airport, while his foes blocked most of the streets leading to the capital’s main square in front of Congress and the presidential palace.
Police urged residents of La Paz to stay in their homes and said they were joining with the army to avoid an escalation of the violence.
Amid the power vacuum, opposition politician and Senate second vice president Jeanine Anez said in an emotional address that she would take temporary control of the Senate, though it was unclear if she would be able to get approval from Congress, which is controlled by supporters of the ex-president.
Additional reporting by Press Association.
