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Soldiers and police directed the evacuation from around the foothills of Mayon volcano amid concerns that a big eruption could occur at any moment.
Philippine officials raised the alert level for Mayon on Monday.
Mayon, 330km (206 miles) south-east of the capital Manila, has erupted 48 times since records began.
The head of the disaster relief operations in the region, Cedric Daep, said the authorities aimed to evacuate nearly 50,000 people from villages within eight kilometres of the volcano by Thursday.
In pictures: Filipinos flee
He said that after a series of ash puffs and ash explosions up to 1,000m high, a major explosion could not be ruled out.