Hybrid multilayer films based on the two molecular species pararosaniline (PR) and Keggin-type polyoxometalate K-5[PMo11VO40)] (PMo11V) were prepared on different substrates using the electrostatic layer-by-layer (LbL) self-assembly method. The film buildup, monitored by electronic spectroscopy, showed a regular stepwise growth, and X-ray photoelectron spectroscopy data confirmed the presence of both molecular components within the LbL films. Scanning electron microscopy images revealed a completely covered surface with a nonuniform distribution of film components, and atomic force microscopy images confirmed a rough surface. The film electrochemical responses and permeability were studied by cyclic voltammetry. Films revealed three Mo-based redox processes (Mo-VI -> Mo-V) and one V-based redox process (V-V -> V-IV) in the potential range between 0.8 and -0.4 V vs Ag/AgCl. Studies with the redox probes [Fe(CN)(6)](3-/4-) and [Ru(NH3)(6)](3+/2+) showed that the films maintain the permeability even after six bilayers. Furthermore, the {PR/PMo11V}n multilayer films exhibit excellent Mo-based electrocatalytic activity toward reduction of iodate and V-based electrocatalytic activity toward ascorbic acid oxidation, thus acting as a versatile multielectrocatalyst.