Ferroelectrics Bi 3.25 La 0.75 (Ti 3−x Nb x )O 12 (BLTN, x = 0 ∼ 0.1) solid solution systems were prepared, and Nb doping effects and relaxor behaviors were investigated. The BLTN single phases were confirmed by XRD. The phase transition temperature decreased as the Nb content increased, and the corresponding dielectric constant maximum broadened. The temperature T m of the dielectric maximum depended on frequency and increased, which indicate that the relaxor behavior was caused by Nb substitution. The substitution of Nb for Ti ions affected the degree of disorder and modified the dielectric properties from those of normal ferroelectrics to relaxor ferroelectrics.