Comparisons are made between polypropylene (PP) fibres and polyacrylonitrile (PAN) fibres in order to relate the thermal properties of fibres with the respective fibre mortar behaviour under thermal exposure. Thermogravimetry (TG), differential scanning calorimetry (DSC) and thermochromatography (ThGC) are utilized. When a cementitious fibre mortar is being heated, several physical phenomena occur in the temperature range between 100°C and 200°C. There is a significant difference in the thermal behaviour between PP and PAN fibres. PP fibres melt at 160–170°C. The non‐melting behaviour of PAN fibre together with its rapid exothermic degradation reactions at around 300°C may add risk to the spalling of fibre mortar under rapid thermal exposure.