Ce(3+)-doped calcium aluminosilicate phosphor was prepared by a combustion-assisted method at an initiating temperature of 600°C. Structural characterization was carried out using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The absorption spectra of Ca2Al2SiO7:Ce(3+) showed an absorption edge at 230 nm. The optical characterization of Ca2Al2SiO7:Ce(3+) phosphor was investigated in a fracto-mechanoluminescence (FML) and thermoluminescence (TL) study. The peak of ML intensity increased as the height of impact of the moving piston increased. The TL intensity of Ca2Al2SiO7:Ce(3+) was recorded for different exposure times of UV and γ-irradiation and it was observed that TL intensity was maximum for a UV irradiation time of 30 min and for a γ-dose of 1180 Gy. The TL intensity had three peaks for UV irradiation at temperatures 82°C, 125°C and 203°C. Also the TL intensity had a single peak at 152°C for γ-irradiation. The TL and ML emission spectra of Ca2Al2SiO7:Ce(3+) phosphor showed maximum emission at 400 nm. The possible mechanisms involved in the TL and ML processes of the Ca2Al2SiO7:Ce(3+) phosphor are also explained.