Cyclic voltammetry, chronoamperometry and chronopotentiometry were used to investigate the electrochemicalbehaviors of Bi(Ⅲ) in Bi(NO3)3-LiClO4-DMSO (dimethylsulfoxide) system on Pt and Cu electrodes. Experimental resultsindicated that the electroreducation of Bi(Ⅲ) to Bi(0) was irreversible on Pt and Cu electrodes. The diffusion coefficient andelectron transfer coefficient of Bi(Ⅲ) in 0.01 mol@ L-1 Bi(NO3)3-0.1 mol@L-1 LiClO4-DMSO system at 303 K were 1.75×10-6cm2@s-1 and 0.147 respectively.