The pick-up driver was taken into custody in hospital, where he was being treated for his injuries, police spokesman Limberth Choque told AFP.
The public prosecutor’s office said the driver was being investigated for possible homicide and causing serious injury.
Forensic experts were combing the accident scene for evidence.
The driver of one of the buses involved in the weekend crash had allegedly been drinking and was speeding when he too swerved into oncoming traffic, prosecutors said.
Six foreigners were among those killed: five Peruvians and a 3-year-old German girl.
Horrific smashes are all too frequent on Bolivia’s narrow, mountain roads.
Road accidents kill an average of 1400 people every year in the country of about 12 million inhabitants, according to government data.
Potosi accounts for 10.6% of all the traffic accidents, according to the Bolivian Observatory of Citizen Security.
More than 120 people have been killed on the department’s roads so far this year.
On February 17, at least 30 people died after a bus plunged into a deep abyss on the outskirts of Potosi.
Authorities said speeding was the suspected cause of that crash.
In January, 19 people died when a bus careened off a road, also near Potosi.
- Agence France-Presse