Micropatterning of organosilane self-assembled monolayers (SAMs) was demonstrated on the basis of photolithography using an excimer lamp radiating vacuum ultra-violet (VUV) light of 172 nm in wavelength. This lithography is generally applicable to micropatterning of organic thin films including alkyl and fluoroalkyl SAMs, since its patterning mechanism involves cleavage of C-C bonds in organic molecules and subsequent decomposition of the molecules. In this study, SAMs were prepared on Si substrates covered with native oxide by chemical vapor deposition in which an alkylsilane, that is, octadecyltrimethoxysilane [CH3(CH2)17Si(OCH3)3, ODS] or a fluoroalkylsilane, that is, 1H, 1H, 2H, 2H-perfluorodecyltrimethoxy-silane [CF3(CF2)7CH2CH2Si(OCH3)3, FAS] were used as precursors. Each of these SAMs was photoirradiated through a photomask placed on its surface. As confirmed by atomic force microscopy and x-ray photoelectron spectroscopy, the SAMs were decomposed and removed in the photoirradiated area while the masked areas remained undecomposed. A micropattern of 2 µm in width was successfully fabricated. Furthermore, microstructures composed of two different SAMs, that is, ODS and FAS, were fabricated as follows. For example, an ODS-SAM was first micropatterned by the VUV-lithography. Since, the VUV-exposed region on the ODS-SAM showed an affinity to the chemisorption of organosilane molecules, the second SAM, i. e. , FAS, confined to the photolithographically defined pattern was successfully fabricated. Due to the electron negativity of F atoms, the FAS covered region showed a more negative surface potential than that of the ODS surface: its potential difference was ca. 120 mV as observed by Kelvin probe force microscopy.