Complex transition metal oxides are distinguished for a close interrelation between their type of crystal structure and electrical and magnetic properties, thus determining their practical importance. Bismuth ferrite based solid solutions contain simultaneously both dipole electric and magnetic ordering thus expanding their potential applications as external impact sensors. The sensitivity of these compositions to external fields is largely dependent on their structural state. 0.65BiFeO3–0.35Ba1-xSrxTiO3 solid solutions (0 ≤ x ≤ 1) the compositions of which are close to the rhombohedral/cubic morphotropic phase boundary have metastable structures and are therefore promising functional materials. The crystal structure and morphology of 0.65BiFeO3–0.35Ba1-xSrxTiO3 solid solutions has been studied using X-ray diffraction, scanning electron microscopy, Raman spectroscopy and energy dispersive X-ray spectroscopy. The chemical substitution of barium ions for strontium ones has been found to reduce the magnitude of rhombohedral distortions and decrease the unit cell parameters for all the substituted compounds. Solid solutions with x ≥ 0,25 have single-phase structure and cubic unit cells, their grain size decreasing with an increase in the concentration of the substituting ions. The results of structural studies obtained using Raman spectroscopy suggest the presence of rhombohedral distortions in the structures of all the compositions studied. The results of structural studies have allowed identifying the sequence of changes in the phase state and lattice parameter of the compounds in the vicinity of the rhombohedral/cubic morphotropic phase boundary. The concentration ranges in which the compounds have single-phase and two-phase structures have been found. The concentration stability range of the polar rhombohedral phase has been corrected on the basis of the structural data obtained using local and microscopic methods.