Biofuel cell electrodes were fabricated by using composite materials consisting of polyaniline/poly(acrylic acid) doped with Au nanoparticles in the form of thin films on a planar Au electrodes. The hybrid films were polymerized on the planar Au electrode surface via electropolymerization, followed by the covalent attachment of amine-terminated Au nanoparticles. The hybrid Au nanoparticles-polymer films were subjected to cyclic voltammetry for the electrochemical oxidation of ascorbic acid and the bioelectrocatalytic activation of glucose oxidase (GOx). It was observed that the incorporation of poly(acrylic acid) with polyaniline shifted its electroactivity to neutral pH, which makes it feasible to use these composite polymers in physiological conditions. Carboxyl groups of poly(acrylic acid) facilitated a facile covalent attachment of GOx and amine-terminated Au nanoparticles onto the polymer films. Furthermore, Au nanoparticles covalently attached onto the polymeric matrix significantly enhanced the charge transport compared to the polymer films without doped Au nanoparticles.