Linear and conjugated poly(p-phenylene ethynylene)s (PPEs) with three different types of functionalized end groups (thiolacetate, isocyanide, and carboxylic acid groups) were synthesized, and their selective chemisorption behavior on various substrate surfaces were investigated using UV/vis transmission absorption spectroscopy. The UV/vis spectra of the PPEs were clearly dependent on the chemical affinity between the PPE end group and the solid surfaces. Furthermore, regarding the chemisorption of thiolacetate modified polymer on a nanoscopic gold particle surface. we visualized novel polymer-colloid nanoarchitectures such as a barbell-type nanohybrid and interconnected polymer nanowire structures that are successively linked through gold nanoparticles.