(Cax,Sr1−x)ZrO3 and Ca(Sny,Zr1-y)O3 solid solutions were synthesized by solid-state reaction at high temperature before to be studied by powder X-ray diffraction and Raman Spectroscopy. Diffraction data allow the distortion of the ABO3 perovskite structure to be investigated according to cations substitution on A and B-sites. It is shown that distortion, characterized by Φ, the tilt angle of BO6 octahedra, slightly increases with decreasing y content in Ca(Sny,Zr1−y)O3 compounds and strongly decreases with decreasing x content in (Cax,Sr1−x)ZrO3 compounds. Such results are discussed in view of the relative A and B cation sizes. Raman data show that vibrational spectra are strongly affected by the cation substitution on A-site; the frequencies of most vibrational modes increase with increasing x content in (Cax,Sr1−x)ZrO3 compounds, i.e. with the decreasing mean size of the A-cation; the upper shift is observed for the 358 cm−1 mode (∂ν/∂r = −60.1 cm−1/Å). On the other hand, the cation substitution on B-sites, slightly affect the spectra; it is shown that in most cases, the frequency of vibrational modes increases with increasing y content in Ca(Sny,Zr1−y)O3 compounds, i.e. with the decreasing mean size of the B-cation, but that two modes (287 and 358 cm−1) behave differently: their frequencies decrease with the decreasing mean size of the B-cation, with a shift respectively equal to +314 and +162 cm−1/Å. Such results could be used to predict the location of different elements such as trivalent cations or radwaste elements on A- or B-site, in the perovskite structure.