A novel biopolymer-based antioxidant, chitosan conjugated with gallic acid (chitosan galloylate, chitosan– GA), is proposed. Electron paramagnetic resonance (EPR) demonstrates a wide range of antioxidant activity for chitosan–GA as evidenced from its reactions with oxidizing free radicals, that is, 1,1-diphenyl-2-picryl-hydrazyl (DPPH), horseradish peroxidase (HRP)–H2O2, carbon-centered alkyl radicals, and hydroxyl radicals. The EPR spectrum of the radical formed on chitosan–GA was attributed to the semiquinone radical of the gallate moiety. The stoichiometry and effective concentration (EC50) of the DPPH free radical with chitosan–GA show that the radical scavenging capacity is maintained even after thermal treatment at 100 °C for an hour. Although the degree of substitution of GA on chitosan was about 15%, its antioxidant capacity, that is, the reaction with carbon-centered and hydroxyl radicals, is comparable to that of GA.