Abstract The (Ca1−xSrx)3(VO4)2 crystals were successfully grown by Czochralski method. Sr3(VO4)2 content in the CVO/SVO solid solution was varied from 10 to 45%, which corresponds to chemical compositions of (Ca1−xSrx)3(VO4)2, 0.1≤ x ≤ 0.45. To obtain crystals of optical quality, bulk crystallization rate was decreased from 0.8 to 0.3 cm3/h for the nominally pure Ca3(VO4)2 crystal and Ca1·8Sr1·2(VO4)2 solid solution, respectively. The Ca2·7Sr0·3(VO4)2, Ca2·4Sr0·6(VO4)2, Ca2·1Sr0·9(VO4)2, Ca1·8Sr1·2(VO4)2, Ca1·65Sr1·35(VO4)2 and Ca1·5Sr1·5(VO4)2 polycrystalline solid solutions were prepared by solid-state synthesis. X-ray diffraction analysis and spontaneous Raman spectroscopy were used for investigation powdered polycrystalline material and grinded single crystals. It was estimated that mono-phase solid solutions with a gradually changing structure parameters are formed in the series (Ca1−xSrx)3(VO4)2 with x = 0.10, 0.20, 0.30, 0.40, 0.45. Further increasing Sr3(VO4)2 content in the CVO/SVO solid solution leads to formation of two-phase system. The influence of the chemical composition on the shape and size of ferroelectric domains for as-grown crystalline materials was shown.