Fully understanding the anisotropic effect of silicon surface orientations in local anodic oxidation (LAO) nanolithography processes is critical to the precise control of oxide quality and rate. This study used ReaxFF MD simulations to reveal the surface anisotropic effects in the LAO through the analysis of adsorbed species, atomic charge, and oxide growth. Our results show that the LAO behaves differently on silicon (100), ( 110), and (111) surfaces. Specifically, the application of an electric field significantly increases the quantity of surface-adsorbed −OH 2 while reducing −OH on the (111) surface, and results in a higher charge on a greater number of Si atoms on the (100) surface. Moreover, the quantity of surface-adsorbed −OH plays a pivotal role in influencing the oxidation rate, as it directly correlates with an increased formation rate of Si−O−Si bonds. During bias-induced oxidation, the (111) surface appears with a high initial oxidation rate among three surfaces, while the (110) surface underwent increased oxidation at higher electric field strengths. This conclusion is based on the analysis of the evolution of Si−O−Si bond number, surface elevation, and oxide thickness. Our findings align well with prior theoretical and experimental studies, providing deeper insights and clear guidance for the fabrication of high-performance nanoinsulator gates using LAO nanolithography.