(Ca1‐xEux)WO4 (x = 0–21 mol%) phosphors were prepared using the classical solid‐state reaction method. The influence of Eu3+ ion doping on lattice structure was observed using powder X‐ray diffraction and Fourier transform infrared spectroscopy. Furthermore, under this influence, the luminescence properties of all samples were analyzed. The results clearly illustrated that the element europium was successfully incorporated into the CaWO4 lattice with a scheelite structure in the form of a Eu3+ ion, which introduced a slight lattice distortion into the CaWO4 matrix. These lattice distortions had no effect on phase purity, but had regular effects on the intrinsic luminescence of the matrix and the f–f excitation transitions of Eu3+ activators. When the Eu3+ concentration was increased to 21 mol%, a local luminescence centre of [WO4]2− groups was detected in the matrix and manifested as the decay curves of [WO4]2− groups and luminescence changed from single exponential to double exponential fitting. Furthermore, the excitation transitions of Eu3+ between different energy levels (such as 7F0→5L6, 7F0→5D2) also produced interesting changes. Based on analysis of photoluminescence spectra and the chromaticity coordinates in this study, it could be verified that the nonreversing energy transfer of [WO4]2−→Eu3+ was efficient and incomplete.
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