In this paper, the optical absorption and radioluminescence (RL) of polycrystalline ceramic and powder CaWO4 are studied. The samples were synthesized via a solid‐state method. Differential thermal analysis and thermogravimetric (DTA/TG) measurements indicate a minimum temperature of 700°C for calcination of precursors. The crystalline phase of the samples of calcium tungstate was investigated by X‐ray diffraction (XRD). The RL of the crystal powder and ceramics are in agreement with that present in the literature for bulk single crystals, presenting a single emission band centered at 420 nm when irradiated with β‐rays. UV‐vis absorption spectroscopy shows that the maximum absorption band of the CaWO4 sample is at around 400 nm, indicating the presence of mixed valence states of W5+ and W6+, associated with a possible breaking of structural symmetry caused by WO4 tetrahedral distortion.