A one-step functionalization process has been developed for oxide-free channels of field effect transistor structures, enabling a self-selective grafting of receptor molecules on the device active area, while protecting the nonactive part from nonspecific attachment of target molecules. Characterization of the self-organized chemical process is performed on both Si(100) and SiO(2) surfaces by infrared and X-ray photoelectron spectroscopy, atomic force microscopy, and electrical measurements. This selective functionalization leads to structures with better chemical stability, reproducibility, and reliability than current SiO(2)-based devices using silane molecules.