The modified glassy carbon electrodes prepared by simultaneously covering with [Os(bpy)2(PVP)10Cl]+redox polymer and Nafion film exhibited excellent electrocatalytic activity for the oxidation of dopamine (DA). Dual linear regions between 1.0x10−8-1.8x10−5M and 1.8x10−5-4.0x10−4M with correlation coefficients of 0.998 and 0.995, respectively, were obtained for log-log plots of catalytic current versus DA concentration. The detection limit for DA determination was ca. 5 nM with 3σ. The dual-film modified electrodes eliminated efficiently the interference from AA presence in a 1000-fold concentration ratio and showed excellent reproducibility for the determination of DA. The modified electrodes have been used to determine DA concentration with both cyclic voltammetric and chronoamperometric techniques. Electrocatalytic kinetics have been studied using a rotating disk electrode. Both the addition of Nafion film and an increase in DA concentration resulted in a decrease in the electrocatalytic rate constant. An apparent Michaelis-Menten constant of 1.3 mM and maximum catalytic current of 88μA were evaluated from the chronoamperometric measurements.