In complex perovskite-type oxides which have been studied as cathode materials, the thermal expansion coefficient increases with the increase in the oxygen ionic conductivity. In the present study, with the aim to explain such a behavior, a research has been carried out from a chemical bond point of view. For oxides A1-xA′xB1-yB′yO with perovskite structure, the ionicity of the individual bond, A-O and B-O, and the thermal expansion coefficient of mixed compounds were estimated by using semiempirical methods. It has been shown that the thermal expansion coefficient and the oxygen ionic conductivity decrease with the increase in the difference of the ionicity between A-O and B-O bonds. It is also found that the tolerance factor and the specific free volume are linearly correlated with the difference of ionicity.