The present work studies europium-ion spectroscopic features in solid solutions based on silicate-tungstates Ca2La6.8Eu1.2Si5.6W0.4O26.4 and Ca8Eu2Si3W3O26 microcrystalline powders with the crystal structure of silicate apatite and scheelite respectively. The spectroscopic features were studied by means of photoluminescence spectroscopy and X-ray excited luminescence at temperatures 4.6, 90 and 295 K. In Ca2La6.8Eu1.2Si5.6W0.4O26.4 only intensive luminescence was observed, which was characterized by a set of 5D0 → 7FJ dominant intraconfigurational transitions for Eu3+ ion. In Ca8Eu2Si3W3O26, both 5D0→ 7FJ intraconfigurational transitions for Eu3+ ion and wide 430 nm emission band corresponding to host self-trapped exciton (STE) emission are observed. This STE emission band is reabsorbed by the f – f absorption of Eu3+ ions by means of energy transfer from host to Eu3+. The asymmetry coefficient which characterizes the shape of the emission spectrum of Eu3+ ions strongly depends on the energy of exciting photons. The Eu3+ ion might occupy two nonequivalent crystallographic sites. Some features of this phenomenon were discussed.