The dielectric-semiconductor interfacial interactions critically influence the morphology and molecular ordering of the organic semiconductor molecules, and hence have a profound influence on mobility, threshold voltage, and other vital device characteristics of organic field-effect transistors. In this study, p-channel small molecule/polymer (evaporated pentacene and spin-coated poly(3,3'''-didodecylquarterthiophene) - PQT) and n-channel fullerene derivative ({6}-1-(3-(2-thienylethoxycarbonyl)-propyl)-{5}-1-phenyl-[5,6]-C61 -TEPP-C61) show a significant enhancement in device mobilities ranging from similar to 6 to similar to 45 times higher for all classes of semiconductors deposited on sol-gel silica gate-dielectric than on pristine/octyltrichlorosilane (OTS)-treated thermally grown silica. Atomic force microscopy, synchrotron X-ray diffraction, photoluminescence/absorption, and Raman spectroscopy studies provide comprehensive evidences that sol-gel silica dielectrics-induced enhancement in both p- and n-channel organic semiconductors is attributable to better molecular ordering/packing, and hence reduced charge trapping centers due to lesser structural defects at the dielectric-semiconductor interface.