Self-assembled monolayers (SAMs) of the alkylthiols with [Os(bpy)3]2+ moiety at the terminal position were prepared on gold electrode surface. Examination of the cyclic voltammograms for the SAM shows that it does not organiz e well unlike alkylthiols, which is attributed to the much larger diameter of [Os(bpy)3]2+ moiety compared with the cross-section of alkyl chains and the distance between the adsorption sites. Electromicrogravimetry study shows that the hydration numbers of the electrolyte were 16 $pm2$, 11 $pm1$, 5 $pm$ 1 and 24 $pm6$ for ClO4- , PF6-, NO3- , and SO42- , respectively. The binary SAMs of alkylthiols with [Os(bpy)3]2+ terminal-group were prepared by co-adsorption of alkylthiols as spacer molecules, which results in better packing in SAM and accordingly the stability was enhanced.