The ferroelectricity of Bi3.2Sm0.8Ti3O12 (BST) and Bi3.2Sm0.8Ti2.97V0.03O12 (BSTV)ceramics prepared at 1100oC by a conventional ceramic technique is investigated. These ceramics possess random-oriented polycrystalline structure. The remanent polarization (Pr) and coercive field (Ec) of the BST ceramics are 16 µC/cm2 and 62kV/cm, respectively. Furthermore, V5+ substitution improves the Pr value of the BST ceramics up to 25µC/cm2, which is larger than that of the BST ceramics. Therefore, the co-substitution of Sm3+ and V5+ in Bi4Ti3O12 (BIT) ceramics is effective for the improvement of its ferroelectricity.