Rigid-rod-type conjugated oligo-p-phenylene vinylenes (OPVs) with terminal hydroxide (-OH) and alkyne (-C„kCH) functionality were attached to Si(100) surfaces via a covalent Si-O-C bonds. One approach involved the reaction of -OH functional oligomers with Si(100)-H and/or Si(100)-Cl functionalized surfaces. Subsequent reaction of the Si(100)-OPV-OH surface with p-tolyl isocyanate produced urethane containing monolayers in a "click chemistry" reaction. A second approach involved the synthesis of Si(100)-OCH2CH2N3 functionalized surfaces starting from the Si(100)-H and/or Si(100)-Cl functionalized surfaces and HOCH2CH2N3, and then using more "click chemistry" to react these Si(100)-OCH2CH2N3 functional surfaces with -C„kCH functional OPV. The monolayers were characterized by means of XPS, FTIR/ATR, and AFM. The results represent a further advance in the controlled functionalization of Si-surfaces and lead to implications for a wide variety of potential applications that can use the combination of an inorganic and organic semiconductor.