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Alkali-activated fly ashes have been proposed for various applications where resistance against high temperatures is required, yet several details regarding the response of these materials to heat-exposure need to be clarified. In the present study, heat-induced cracking in fly ash-based alkali-activated pastes and lightweight mortars was analyzed by in-situ acoustic emission (AE) detection during complete heating-cooling cycles (up to ∼1100 °C), augmented by thermogravimetry and ex-situ SEM and XRD analyses. The applicability of the lightweight mortars as passive fire protection coatings was assessed by recording temperature-time curves of mortar-coated steel plates. Cracking during heating was limited and associated exclusively with the dehydration of the materials in the temperature range ∼90–360 °C. However, samples heated to temperatures above ∼600 °C exhibited intense cracking on cooling. This was attributed to differential deformations caused by local sintering and partial melting at the glass transition temperature, and subsequent quenching on cooling.