The chemistry of monolayer-forming organosilane precursors was used to (I) create assembled thin films having custom-designed and engineered surface composition and (2) affect interfiber adhesion and surface charge of individual fiber or fiber-mat. Thin films were formed from three materials: an aminoalkyl silane (SIL), a perfluorinated alkylsilane (F3), and alkyl trimethoxysilyl ammonium chloride (CAT), and were characterized by X-ray photoelectron spectroscopy (XPS) measurements. Exposed surfaces were then heat-treated to reduce amine functionality and increase hydroxyl functionality. The thin film deposits were used to spatially control the interfiber adhesion and surface charge of lignocellulosic fiber and fiber-mat. Development of ultrathin film on fiber surface was observed to be chemical in nature, which suggests that conformational states of the surface functionality controlled the deposition of molecules.