The symmetrical volcano is on the shores of Lake Villarica, by the town of the same name. The region is a tourist hotspot, annually attracting thousands of people who climb the nearby hills and hike in the surrounding forests.
According to ONEMI, 2100 people have been evacuated from the town of Pucon - one of the most popular tourist towns in Chile and a centre for outdoor sports.
In the Villarica district, 20 people have been evacuated, while a further 1000 people have left the district of Panguipulli.
"It was the most amazing thing I've ever seen," 29-year-old Australian tourist Travis Armstrong said from Pucon.
"I've never seen a volcano erupt and it was spewing lava and ash hundreds of metres into the air. Lightning was striking down at the volcano from the ash cloud that formed from the eruption."
Chile has more than 2000 volcanoes, of which 91 are active. It is the second most volcanically active country in the world, after Indonesia.
And the eruption came as a team of film-makers released footage from Vanuatu captured on a drone camera, showing the inside of the Marum Crater on Ambrym Island.
- AP