Direct benzoylation of the two hydroxyl groups on chitosan was achieved using a phosphoryl mixed anhydride system, derived from trifluoroacetic anhydride (TFAA), benzoic acids (BAs), and phosphoric acid (PA). The reaction is operated as a one pot process under mild conditions that does not require neither an inert atmosphere nor dry solvents. The structures of the synthesized compounds were confirmed by NMR and IR spectroscopy. Solubility tests on the products revealed that they were soluble in organic solvents such as N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), and acetone. In the meantime, a morphological study by scanning electron microscopy (SEM) evidently indicated that the chitosan benzoates underwent significant structural changes after the benzoylation.