Selenium nanoparticles of 1020 nm in diameter have been prepared using cellulose nanocrystal (CNXL) as a reducing and structure-directing agent under hydrothermal conditions. Na2SeO3 was reduced to form elemental selenium nanoparticles under hydrothermal conditions. During the hydrothermal process (120160 °C), CNXL rods were mainly maintained and selenium nanoparticles were interfacially bound to the CNXL surface. The reaction temperature affects the sizes of interfacially bound selenium nanoparticles. X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), and transmission electron microscope (TEM) were employed to characterize interfacially bound selenium nanoparticles on CNXL surface.