The electrochemical properties of eight new divalent transition metal benzenesulphonate complexes with 1,10-phenanthroline in different solvents and supporting electrolytes were investigated by means of cyclic voltammetry(CV). Based on the CV data the influences of various coordination modes on the electrochemical behavior of the complexes were discussed. The diffusion coefficient Dc and rate constant ks of those complexes in DMF systems were estimated according to CV and the results show that these processes were all quasi-reversible.