Phosphorylated chitosan membranes were prepared from the reaction of orthophosphoric acid and urea on the surface of chitosan membranes in N,N‐dimethylformamide. Their ionic conductivity in the wet state was investigated. Chemical modifications contributed to improved ionic conductivities of the chitosan membranes. Compared to the unmodified chitosan membranes, it was found that hydrated phosphorylated chitosan membranes with an appropriate phosphorus content showed an increasing ionic conductivity of about one order of magnitude. The phosphorylation reaction mechanism was explained based on 13C and 31P NMR measurements. It was also observed that the crystallinity of the phosphorylated chitosan membranes and the corresponding swelling indices were changed pronouncedly, but these membranes did not lose either their tensile strength or thermal stability to a significant degree in comparison with the unmodified chitosan membranes.