Crystalline self-assembled monolayers (SAMs) of organosilane compounds such as octadecyl-trimethoxysilane (OTMS) and octadecyltrichlorosilane (OTCS) were deposited by a simple, spin-casting technique onto Si/SiO₂ substrates. Fabrication of the OTMS SAMs and characterization using ellipsometry, contact angle, atomic force microscopy (AFM), grazing angle attenuated total reflectance Fourier transform infrared (GATR-FTIR) spectroscopy and grazing incidence X-ray diffraction (GIXD) are described. The characterization confirms that these monolayers exhibit a well-packed crystalline phase and a remarkably high degree of smoothness. Semiconductors deposited by vapor deposition onto the crystalline OTS SAM grow in a favorable two-dimensional layered growth manner which is generally preferred morphologically for high charge carrier transport. On the OTMS SAM treated dielectric, pentacene OFETs showed hole mobilities as high as 3.0 cm ²/V·s, while electron mobilities as high as 5.3 cm ²/V·s were demonstrated for C₆₀.