Novel solid films of a mixed polynuclear hexacyano iron(III) and decavanadates have been electrochemically prepared. The colour of these solid thin films ranged from yellow to blue depending on the thickness. The cyclic voltammograms (CVs) of these solid films indicate the involvement of both vanadium and iron redox centres in performing the electrochemical activities. Evidence of the catalytic activities of these films towards the reduction of some small oxoanions has been reported.