This paper reports a simple method for the multilayer immobilization of conjugated polymers, gold nanoparticles on solid supports. Poly(phenyenevinylene) functionalized with aldehyde and aminooxy groups was chemoselectively immobilized onto both glass and gold substrates via layer-by-layer deposition. The physical properties of the thin films were characterized by grazing angle IR, TM-AFM, fluorescence, and UV-visible spectroscopy. This methodology was also successfully applied to prepare polymer/gold nanocluster alternating multilayers. The results show that this methodology provides a general route for preparing robust and functionalizable multilayer films on solid substrates with molecular-level thickness control.