Cellulose nanofibers (CNFs) with an average diameter 8 nm were isolated from corncobs using a stepwise method that included steam-explosion pretreatment, alkaline treatment, sodium hypochlorite bleaching, high-speed blending, and ultrasonic treatment. This mechanochemical method used only two chemical reagents in low concentrations to remove non-cellulosic components. The removal of non-cellulosic components was confirmed by Fourier-transform infrared spectroscopy. X-ray diffraction revealed an increase in crystallinity during steam explosion and subsequent mechanochemical treatments. Pretreatment by steam explosion caused the partial hydrolysis of hemicellulose and loosened the structure of raw materials, which facilitated the subsequent chemical processes. The thermal stability and morphology of samples at different stages were also investigated. Steam explosion increased the thermal stability of hemicellulose and cellulose components, as it removed a fraction of hemicellulose. High-speed blending reduced the entanglement of cellulosic fibers and created uniform size. Ultrasonic treatment was used in the final step of nanoscale fibrillation. The method used in this study is environmentally friendly and has the potential to be applied at industrial scale.