AbstractAs the main raw material for fiberboard, the hygroscopicity of wood fibers is of great concern. In this study, three alkoxysilanes with different chain lengths—methyl trimethoxy silane (MTMS), octyl trimethoxy silane (OTMS), and dodecyl trimethoxysilane (DTMS)—were used respectively to treat wood fibers to reduce their hygroscopicity and surface hydrophilicity. After alkoyxilane properties were evaluated, the chemical structures, surface groups, and morphology and distribution of alkoxysilanes within modified wood fibers were characterized using scanning electron microscopy (SEM) coupled with energy-dispersed X-ray analyzer (EDXA), Fourier Transform Infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The study found that after modification, the moisture adsorption rate of wood fibers had decreased and the surface hydrophobicity of the fibers had been promoted. The fibers modified with MTMS adsorbed the least amount of moisture. The study also found that while hydrolyzed silane penetrated into wood fibers and reacted with their chemical components, long chains of the silane hindered the degree of that penetration.