Electrodeposition of silver on a poly(o-aminophenol) (POAP) modified platinum electrode was studied by using cyclic voltammetry and chronoamperometry techniques. Results suggest that this process occurs at the polymer I electrode interface. The polymer film is rather indifferent to the electrodeposition of silver because of the low conductivity of the film at potentials where crystallization occurs. Experimental transients indicated that at very short times the process follows a three-dimensional and progressive nucleation pattern with diffusion controlled growth. At pH 5, the formation of silver-polymer amino-complexes may take place.