Silicon wet bulk micromachining is the most widely used technique for the fabrication of diverse microstructures such as cantilevers, cavities, etc. in laboratory as well as in industry for micro-electromechanical system (MEMS) application. Although, increasing the throughput remains inevitable, and can be done by increasing the etching rate. Furthermore, freestanding structure release time can be reduced by the improved undercutting rate at convex corners. In this work, we have investigated the etching characteristics of a non-conventional etchant in the form of hydroxylamine (NH2OH) added sodium hydroxide (NaOH) solution. This research is focused on Si{100} wafer as this orientation is largely used in the fabrication of planer devices (e.g., complementary metal-oxide semiconductors) and microelectromechanical systems (e.g., inertial sensors). We have performed a systematic and parametric analysis without and with 12% NH2OH in 10 M NaOH for improved etching characteristics such as etch rate, undercutting at convex corners, and etched surface morphology. 3D scanning laser microscope is used to measure average surface roughness (Ra), etch depth (d), and undercutting length (l). Morphology of the etched Si{100} surface is examined using optical and scanning electron microscopes. The addition of NH2OH in NaOH solution remarkably exhibited a two-fold increment in the etching rate of a Si{100} surface. Furthermore, the addition of NH2OH significantly improves the etched surface morphology and undercutting at convex corners. Undercutting at convex corners is highly prudent for the quick release of microstructures from the substrate. In addition, we have studied the effect of etchant age on etching characteristics. Results presented in this article are of large significance for engineering applications in both academic and industrial laboratories. © 2022, The Author(s).