The oxidation and reduction of the conductive polymer polypyrrole (PPy) doped with different counterions (bromide, ferrocyanide (FCN) and poly(p-styrenesulfonate)) was studied by scanning electrochemical microscopy (SECM) during both potential step (chronocoulometric) and cyclic voltammetric scans. The ultramicroelectrode tip was positioned close to the surface of a PPy-modified substrate electrode, and the responses of both electrodes to a substrate potential step or linear sweep were monitored simultaneously. In this way, the rates of bromide or ferrocyanide ejection during PPy reduction were shown to be functions of the reduction potential. The nature of the cation (e.g., TBA(+) vs K+) was an important factor determining the kinetics of ion transport in the PPy(+)/FCN- films. With a solution containing TBA(+) the release of Fe(CN)(6)(4-) during PPy(+)/FCN- reduction was kinetically slow, and some ferrocyanide-containing species were also ejected during film reoxidation. Direct evidence for the incorporation of cations (e.g., Ru(NH3)(6)(3/2+)) in a PPy film during its reduction was also obtained by SECM measurements. Finally, the physical localization and mechanism of Fc(+) (Fc = ferrocene) and Os(bpy)(3)(3+) (bpy = 2,2’-bipyridine) reduction at oxidized and reduced PPy are discussed in connection with the applicability of different models for conducting polymers.