Airlines cancelled flights as the towering, mushroom-shaped ash cloud rose from Calbuco's snowy peak.
Schools also suspended classes in the region.
Television images showed large traffic jams and long lines at petrol stations in Puerto Montt, where a red alert was declared, along with nearby Puerto Varas.
"I would like to call on the population to remain calm and stay informed," said Interior Minister Rodrigo Penailillo. "The police have given orders and begun to evacuate."
The initial evacuation involved about 270 families, but could be expanded, officials said. Calbuco had been inactive for 43 years.
It was a "rather explosive eruption", said Gabriel Orozco, a volcanologist at the National Geology and Mines Service.
He said the 10km-high ash cloud risked collapsing, and warned: "River beds are very dangerous at the moment" because of the risk of ice and snow melting and causing floods.
-AAP