Composite materials consisting of polyaniline/poly(4-styrene-sulfonate) (PAn/PSS) or polyaniline/Au nanoparticles capped with 2-mercaptoethane sulfonic acid (PAn/Au-NPs) are prepared in the form of thin films (thickness ca. 90 nm) on Au electrodes or in the form of microrods linked to a Au surface. The composite materials in the microrod structures are electrochemically prepared in porous alumina membranes coated with a Au film, followed by the dissolution of the membrane. Chronoamperometric experiments reveal that the charge transport in the PAn/Au-NPs system is ca. 25-fold enhanced as compared to the analogous PAn/PSS system. The different polyaniline composite assemblies were used as catalysts for the electrochemical oxidation of ascorbic acid and as electron-transfer mediators for the bioelectrocatalytic activation of glucose oxidase (GOx) toward the oxidation of glucose. The PAn/Au-NPs system in the microrod structure reveals superior function as the catalyst for the electrochemical oxidation of asco...