Thin films of vapor-phase polymerized PEDOT incorporating various cationic Mn porphyrins were assessed for water oxidation catalysis under light illumination. Only Mn(III)TPP/PEDOT displayed a notable photocurrent and this was, counter-intuitively, greatest at the lowest loading levels examined. Studies revealed that a proportion of the Mn(III)TPP within the PEDOT became demetalated during polymerization, leaving free and protonated TPP. Despite the presence of an excess of chemical oxidant during the polymerization step, the Mn(III) ion was reduced — likely under the influence of light — to Mn(II), which was labilized out of the film. Whereas PEDOT films loaded with anionic Mn porphyrins may be active and selective water oxidation photocatalysts, their analogs containing cationic Mn porphyrins, like Mn(III)TPP, are catalytically inert.