Polyethylenimine-capped platinum nanoparticles (PEI-capped Pt NPs) are synthesized by photoreduction and qualified as a component for electrostatic layer-by-layer assembly and subsequent electrocatalysis. The PEI-capped Pt NPs are characterized for size and charge using scanning force microscopy, transmission electron microscopy, dynamic light scattering and zetapotential. Well-defined multilayers are produced via thin film electrostatic assembly of PEI-capped Pt NPs with the conducting polymer: poly(3,4-ethylenedioxythiophene):poly(p-styrenesulfonate) [(PEDOT:PSS)(-)Na(+)]. The composite thin films are subsequently characterized by ultraviolet-visible spectroscopy, scanning force microscopy, inductively coupled plasma mass spectroscopy and thermogravimetric analysis. The layer-by-layer deposition process was found to proceed in a controlled manner which permits the fabrication of stable and uniform multilayer thin films. [PEI-capped Pt NPs/(PEDOT:PSS)] multilayers were found to be an active catalyst coating for the oxidation of methanol and a 20 bilayer film proceeds with a stable level of catalyst activity for over 1000 oxidation cycles.