Novel inorganic film modified electrodes have been prepared by chemical deposition of a thin palladium pentacyanonitrosylferrate (PdPCNF) film on the surface of aluminum substrate. The modification process including the electroless deposition of metallic palladium on the aluminum electrode surface from PdCl2+25% ammonia solution and chemical derivatization of deposited palladium to the PdPCNF film in 0.1 M Na2[Fe(CN)5NO]+0.5 M KNO3+HNO3 solution (pH 1.5–2.5), are described. The aluminum-based modified electrodes exhibit, one pair of well-defined voltammetric peaks which correspond to the Fe(III)/Fe(II) transition in complex structure. The effect of pH, ammonium, alkali metal and alkaline earth metal cations of supporting electrolyte on the electrochemical characteristics of the modified electrode was studied in detail. Diffusion coefficients of hydrated ammonium and alkali metal cations in the film (D), transfer coefficient (α) and transfer rate constant for electron (k s), were determined. The high stability of this modified electrode makes it attractive in practical application.