This paper presents a systematic photoluminescence spectra study of the (111) growth surface of an opal photonic crystal whose pores were filled with salt Europium (III) acetate monohydrate (C(6)H(9)EuO(6)xH(2)O). Ultraviolet excitation was provided by semiconductor laser operating at wavelengths of 405 nm. Emission spectra were measured both for free-form salt samples and for salt in opal pores annealed at various temperatures up to 1000 degrees C. The influence of changes in the coordination environment of europium ions on the luminescence spectra in the process of dehydration and salt decomposition up to Eu(2)O(3)is established. Differences in the spectra of salt in the pores of opal were revealed compared with the spectra in the free state.