BiFeO3 multiferroic ceramics were modified by introducing CaTiO3. The stability of perovskite BiFeO3 was increased by the present modification, and the single-phase (Bi1 − xCax)(Fe1 − xTix)O3 solid solutions were obtained when x ≥ 0.15, where the symmetry changed from R3c (x ≤ 0.2) to Pbnm (x ≥ 0.3). The ferroelectric property of BiFeO3 was enhanced by introducing CaTiO3 because of the reduction of leakage current and the increase of resistivity. The increased dielectric constant, decreased dielectric loss, and enhanced remnant magnetization Mr were also obtained. The best combination of multiferroic characteristics were achieved at x = 0.2.