Zinc Oxide (ZnO) is actively investigated for hybrid organic inorganic device applications. The interface greatly influences the electronic properties of these devices. Molecular surface modification of ZnO is being investigated for its potential to control the alignment of energy levels, charge transfer, as well as, interfacial chemical characteristics that influence device fabrication. In this study, octadecyltriethoxysilane (OTES) treatments of thin film ZnO produced by sol-gel decomposition were explored. The ZnO films were hydroxylated and then modified using OTES in solution. The condensation reaction of the OTES at the surface was promoted by the addition of a protoamine catalyst. Contact angle and infrared spectroscopy studies confirmed the surface modification and indicated that the coverage of the OTES was submonolayer. The modified ZnO films were reproducible and stable for long periods. The effects of the modification on subsequently spin-cast poly[3-hexylthiophene](P3HT) and on hybrid ZnO/P3HT organic solar cell performance are discussed.