Barium titanate (BaTiO3, BT) – bismuth titanate magnesium oxide (Bi(Mg0.5Ti0.5)O3, BMT) solid solution system ceramics were prepared by conventional sintering method in pursuit of the enhancement of the BT Curie temperature (TC, 132 °C). Normal ferroelectric polarization vs. electric-field (P-E) hysteresis loops were observed for BT-BMT ceramics with BMT contents below 20 and above 60 molar%. On the other hand, broad P-E double hysteresis loops were observed for BMT contents from 30 to 50 molar%. The origin was investigated using synchrotron XRD measurement and Rietveld analysis. The crystal structure was assigned to ferroelectric phase with domain-pinning by certain defect structures. A modified phase diagram was proposed on the basis of the temperature dependence of the crystal structure.