The fabrication, structure, electrochemical properties, and electrocatalytic properties of a manganese(III-)substituted Dawson-type phosphopolyoxotungstate, alpha(2)-K7P2W17O61(Mn3+.OH2).12H(2)O (P2W17Mn), entrapped in polypyrrole (PPy) film have been studied. The hybrid film was prepared by potentiostatic polymerization from aqueous solution containing 20 mM pyrrole (Py) and 2 mM P2W17Mn on a pyrolytic graphite (PG) surface. Chronoamperometry, Raman spectroscopy, UV-visible absorption spectroscopy, and cyclic voltammetry were used to monitor and characterize the growth, structure, and properties of the film. The chronoamperometric curve shows that P2W17Mn can catalyze the electrochemical polymerization of Py. The Raman spectrum suggests that the doped P2W17Mn has little effect on the structure of PPy film. The P2W17Mn/ PPy film exhibits good voltammetric response in both the acidic aqueous and acetonitrile solutions. At pH 1.0, the molar ratio of pyrrole to P2W17Mn7- in the hybrid film is 21.1:1, quite close to the expected ratio of 21.2:1 for a PPy film with a +0.33 oxidation level per pyrrole moiety and doped with an anion with a charge of 7. The influence of solution pH on P2W17Mn7- in the film is much smaller than that in the aqueous solution. During the potential scanning in 0.1 M LiClO4. acetonitrile solution, P2W17Mn7- was slowly released from the hybrid film and electrolyte ions (Li+ and ClO4-),were inserted into the film. This was identified by cyclic voltammetry and UV-visible spectroscopy. Additionally, the hybrid film can effectively catalyze the reduction of hydrogen peroxide and nitrite.