Solid solutions of phosphate-vanadates Ca9La(PO4)7(1–x)(VO4)7x:Eu3+(1 %) with the structure -Ca3(PO4)2 activated by europium were synthesized by the standard solid-phase method. It is shown that a continuous series of solid solutions is formed upon substitution P5+ → V5+. At the same time, the study by the second harmonic generation method showed that a symmetry inhomogeneity is observed in the series. When studying the luminescent properties, standard transitions of the europium cation with the dominant electric dipole transition 5D0 → 7F2 were found. The most intense emission was demonstrated by compositions with a centrosymmetric structure.