The mechanoluminescence (ML) and thermoluminescence (TL) of γ-irradiated CaSO4:Eu phosphor have been studied. CaSO4 samples having different concentrations of Eu were prepared by dissolving CaSO4·2H2O in sulphuric acid and evaporating the excess acid around 300 °C. ML was excited impulsively by dropping a load onto the sample. Three distinct peaks have been observed in the ML intensity versus time curve. The ML intensity increases with the increasing concentration of the dopant. The effect of temperature on the shape and peak of ML intensity was also recorded. Growth, saturation and broadening in an ML peak were observed. TL glow curves of CaSO4:Eu phosphors at different concentrations contain two TL peaks: the first peak was observed at around 110 °C and the other at 210 °C. Experimental results suggest that the ML excitation is related to the movement of dislocation with defect centres, the increase in ML with temperature is due to the enhancement in dislocation capture probability, and the reduction is due to the thermal bleaching of defect centres.