The oxidative polymerization of N-glucosylaniline was carried out using ammonium persulfate as the oxidant in phosphate buffer. The structure of the isolated polymer was determined by H-1 NMR, C-13 NMR, and UV-vis spectroscopy to be the polyaniline having glucose residues attached to the general polyaniline unit. Participation of the ortho-position of the aromatic ring in the polymerization was also confirmed by the analyses.