The present work has attempted to prepare platinum–copper (Pt–Cu) and platinum (Pt) nanoparticle-deposited poly(sulfonyldiphenol/cyclophosphazene/benzidine)–graphene oxide catalysts for the electrochemical oxidation of alcohols and single stack direct alkaline alcohol fuel cells. Electrochemical performance of methanol and ethylene glycol is measured using Pt–Cu/poly(SDP/CP/BZ)–GO and Pt/poly(SDP/CP/BZ)–GO catalysts as the working electrode in KOH solution using cyclic voltammetry analysis. Platinum–copper and platinum nanoparticles embedded with the poly(SDP/CP/BZ)–GO composite show enhanced electrooxidation current, lower onset potential and good CO tolerance compared to that of Pt/GO and Pt/poly(SDP/CP/BZ) catalysts. Further, the Pt–Cu/poly(SDP/CP/BZ)–GO catalyst exhibits enhanced catalytic activity with respect to lower onset potential and higher oxidation current than that of the Pt/poly(SDP/CP/BZ) catalyst. Hence, single stack direct alcohol alkaline fuel cells are constructed using the Pt–Cu/poly(SDP/CP/BZ)–GO catalyst as an electrode material. The optimum power densities of 112.24 and 140.67 mW cm⁻² are observed for methanol and ethylene glycol in single direct alkaline alcohol fuel cells.