Perovskite-structured solid solutions intended for use as microwave dielectric resonators were studied by Raman spectroscopy. Two distinct categories were investigated: (i) simple perovskite–simple perovskite solid solutions, that is, CaTiO3–SrTiO3 (CTST), CaTiO3–CaZrO3 (CTCZ), CaTiO3–NdAlO3 (CTNA), and CaTiO3–LaGaO3 (CTLG); and (ii) simple perovskite–complex perovskite solid solutions, such as CaTiO3–SrMg1/3Nb2/3O3 (CTSMN). In the latter category, the influence of A-site ion radius was also addressed by examining 0.5CaTiO3– 0.5LaMg1/2Ti1/2O3 (0.5CT–0.5LMT), 0.5SrTiO3 (ST)–0.5LMT, and 0.5BaTiO3 (BT)–0.5LMT. Raman data from the end members and solid solutions are compared, paying particular attention to F 2 g and A 1 g mode bands, often associated with ordering of B-site species.