Electrochemical properties of composite films consisting of polyaniline/carboxydextran (PANI/carDEX) as a biofuel cell electrode platform were investigated. These composite films were formed on a planar gold surface through electropolymerization after a simple chemical modification of dextran with carboxyl groups. Cyclic voltammetry indicated that the composite films retained a redox activity in neutral pH environment. The PANI/carDEX composite films showed an electrocatalytic activity for the oxidation of ascorbic acid. The PANI/carDEX composite films also demonstrated an excellent electron-transfer mediating capability for the bioelectrocatalytic activation of glucose oxidase (GOx) toward the oxidation of glucose.