Multiferroic BiFeO3/Bi3.25Sm0.75Ti2.98V0.02O12 double-layered thin films on Pt/Ti/SiO2/Si were fabricated using the pulsed-laser deposition technique. The films showed greatly enhanced ferroelectric and ferromagnetic properties. The values of the remanent polarization (2Pr) and coercive field (Ec) were 71.8 µC/cm2 and 148 kV/cm at a maximum applied voltage of 13 V, respectively. The value of the magnetic moment was found to be 17.5 emu/cm3. The enhancement of the polarization originated from the BiFeO3 with Bi3.25Sm0.75Ti2.98V0.02O12 working as a barrier layer. The enhancement of the magnetization is from the structural distortion of BiFeO3, due to partial epitaxial growth on the bismuth titanate surface.