An effect of addition of CaO on electrical resistivity in BaTiO3-(Bi1/2Na1/2)TiO3(BT-BNT) solid solution ceramics was investigated. Three kinds of CaO adding processes were applied. Extra CaO additive against stoichiometric composition is effective to give semiconductive property into the BT-BNT ceramics. However, the ceramics with CaO-inclusive composition such as Ba0.9(Bi0.5Na0.15Ca0.35)0.1TiO3had a high resistivity. From chemical composition analysis and structure analysis, it was concluded that Ca2+dominantly substituted for Na+in theAsite of perovskite-typeABO3structure and then that residual Bi3+acts a donor.