Through 172 nm vacuum ultraviolet light irradiation in a high vacuum condition (HV-VUV), well-defined micropatterns with a varied periodic friction were fabricated at the surface of self-assembled monolayers (SAMs) terminated with oxygenated groups. No apparent height contrast between the HV-VUV-irradiated and -masked areas was observed, which indicated the stability of the C-C skeleton of the assembled molecules. The trimming of oxygenated groups occurred through dissociating the C-O bonds and promoting the occurrence of α- and β-cleavages in the C═O-containing components. Hence, the HV-VUV treatment trimmed the oxygenated groups without degrading the C-C skeleton. The HV-VUV treatment influenced the order of the assembled molecules, and the step-terrace structure was distorted. The decrease in friction at the HV-VUV-irradiated domains was attributed to the dissociation of oxygenated groups. (3-Aminopropyl)trimethoxysilane (APTMS) aggregated at the masked areas of the HV-VUV-patterned SAM, where the oxygenated groups worked as anchors. APTMS aggregations did not exist at the irradiated areas, indicating the trimming of the oxygenated groups at these areas. The direct assembling of APTMS on the Si substrate at the irradiated areas was prevented by the remaining C-C skeleton.