Perovskite solid solution ceramics of (1 − x)BiFeO3–xBaTiO3 (1 − x)BF–xBT, 0.2 ≤ x ≤ 0.45) with high electrical resistivity were prepared by solid-state reaction method. Actual ferroelectric hysteresis loops and temperature dependence of dielectric constant of the ceramics were obtained. Ceramics of 0.7BF–0.3BT with small rhombohedral distortion show highest remnant polarization (Pr = 26.0 μC/cm2) and piezoelectric coefficient (d33 = 134 pC/N). Compositions with pseudo-cubic symmetry (intermediate phases) show relaxor-like dielectric anomaly. The values of Pr and d33 decrease with increasing BT content, from 24.8 μC/cm2 and 104 pC/N for 0.65BF–0.35BT to 8.2 μC/cm2 and 5 pC/N for 0.55BF–0.45BT.