Cobalt and manganese phthalocyanines were characterized by abrasive stripping voltammetry. Traces of the pigment powders were mechanically transferred to the surface of a paraffin-impregnated graphite electrode and investigated by cyclic and square-wave voltammetry. The responses of four major redox couples were identified : Co(II)/Co(III), Co(II)/Co(I), Mn(II)/Mn(III) and Mn(II)/Mn(I). Their redox reactions were accompanied by the simultaneous inclusion or expulsion of K+ or NO3- ions into or from the crystal structure, which was demonstrated by the electron microprobe analysis. Catalytic effects on the electroreduction of oxygen were demonstrated.