Like polyaniline (PAn), electrodeposited films of poly-o-aminophenol (POAP) of different thicknesses, and hence different oxidation states, were found to react differently with a 0.1 M aqueous solution of AgNO3. The interactions between Ag+ and POAP ranged from redox reactions in which the cations were reduced to the metallic form upon contact with the polymer, to a partial charge transfer between metal and polymer resulting in the formation of a metal-polymer complex. These two types of interaction predominated in thick and thin films respectively, and films of moderate thickness exhibited intermediate behaviour. The interactions are believed to originate from a silver-nitrogen linkage moderated by the presence of oxygen from the -OH group, As POAP is more resistant to electrochemical degradation and can take up four times as much silver as PAn through the metal-polymer interactions, practical applications may be developed to exploit such properties.