11-mercaptoundecanoic acid (MUA) monolayer and MUA-copper ion-MUA bilayer assembled using thiolate-copper ion-carboxylate bridges on MUA monolayer electrode were prepared, and tried to control electron transfer rate of redox ions. The soaking solution to assemble MUA on gold electrode changed from ethanolic MUA solution to 1-butanolic one, then the 2 2 differential interfacial capacitance decreased from 2.5+/-0.1 muF cm(-2) to 1.6+/-0.2 muF cm(-2), and electron rate constant, k(0) of [Co(phen)(3)](3+) decreased from 20 x 10(-6) cm s(-1) to 8.3 x 10(-6) cm s(-1). These results show that highly ordered MUA monolayer can be obtained only changing soaking solvent to assemble MUA, Obtained highly,ordered MUA monolayer electrode was block off completely redox anion by electrostatic repulsion and MUA film thickness. Moreover using MUA-copper ion-MUA bilayer electrode, k(0) of [Co(phen)(3)](3+) decreased under 1/400 against using MUA monolayer electrode, that value become to under 0.02 x 10(-6) cm s(-1). This study shows that the combination of electrode surface charge and length of. insulating spacers is able,to control electron transfer rate of various electroactive ions.