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Fire crews received multiple calls to the former Karoro Learning site on Tainui St, next to Dixon Park at about 2.30pm.
Images show large plumes of smoke coming from the building.
Forty firefighters from Greymouth, Cobden, Runanga and Brunner are currently dampening down and decontaminating due to asbestos in the building.
Greymouth chief fire officer Lee Swinburn said the block of four classrooms measuring about 12 by 35 metres was well alight on arrival.
He said the building suffered substantial smoke and water damage and the it will not be able to be saved.
A police scene guard will be onsite overnight.
Swinburn says police and fire investigators will be onsite tomorrow morning.
In 2020, a suspicious blaze damaged an old empty school building on the site.