The electrified production of hydrogen peroxide (H2O2) by oxygen reduction reaction (ORR) is attractive to increase the sustainability of chemical industry. Here the same chains of intrinsically conductive polymer, poly(3,4-ethylenedioxythiophene) (PEDOT) are utilized, as ORR electrocatalyst, while varying polymeric primary dopants (PSS and Nafion) and the level of secondary doping with DMSO. These changes modulate various properties of the film, such as its microscale organization and electronic conductivity. The aim here is to clearly decouple the rate of the heterogeneous electron transfer (HET) of ORR from the diffusion affected by electronic conductivity and the electrochemically available surface area. It is found that the rate of HET and the double layer capacitance are significantly affected by primary dopant. On the contrary, secondary doping shows very little effect on the rate of HET. However, such secondary doping resulted in the increase of both electrochemically available surface area and the diffusion through the polymer film. This effect is attributed to a few orders increase of the electronic conductivity in the film improving availability of the polymer for electron transfer. The enhancement of diffusion upon the secondary doping of conducting polymer is utilized to improve direct conversion of air into H2O2 on gas diffusion electrode.