The surface modification of carbon nanomaterials with heteroatoms improves their electrocatalytic activity for oxygen reduction reaction (ORR). The present work reports the surface modification of carbon nanofiber (CNF) with poly(diallyldimethylammonium) chloride (PDDA) and Triton X-100. PDDA behaves as an electron-acceptor, and the intermolecular charge transfer from CNF to PDDA creates delocalized positive charge sites at the edge and basal plane sites of CNF. Triton X-100 disperses CNF, but also acts as a masking agent to obstruct the intermolecular charge transfer between CNF and PDDA. The surface modification of CNF with (PDDA + Triton X-100) is characterized in terms of FESEM, TEM, EDX, Raman, FTIR and TGA. The electrocatalytic activity of the conjugated systems (CNF + PDDA and CNF + Triton X-100+PDDA) is investigated in terms of cyclic voltammetry and linear sweep voltammetry. The reduction of oxygen at PDDA-CNF occurs via a more efficient four-electron (n = 3.9) pathway in 0.1 M KOH and exhibits a limiting diffusion current density of 3.23 mA cm-2, which is closer to the Pt/C electrode (3.41 mA cm-2). PDDA-CNF even outperforms PDDA-CNT or graphene for the ORR performance owing to their special morphological features. This study thus provides a facile and viable strategy for the scalable production of CNF based ORR electrocatalysts.