The authors in this study used the sol-gel process to prepare Bi-doped TiO2 as a novel electrocatalyst. Results show that Bi can be doped successfully into TiO2 from 1%to 90%. The electrical conductivity of a 1%Bi-doped TiO2 particle-suspended solution is increased nearly twice that of pure TiO2. The electro-catalyzing property of the synthesized Bi-doped TiO2 catalyst was performed under acidic conditions toward a methyl blue dye solution. The observed removal percentage of methyl blue dye was from 5%to 75%. The optimized electro-catalyzing condition was observed at 5%Bi-doped TiO2 with a working voltage of 5 V.