An easy handling infrared measurement, grazing angle mirror-backed reflection (GMBR), has been established to analyze the silicon-based organic monolayer. Theoretical prediction gave the optimal configuration with p-polarized irradiation near a grazing angle 78.1 degrees of incidence. Experimental measurement of hydrogen-terminated, undecylenic acid (UA) and N-hydroxysuccinimide (NHS) functionalized silicon (111) surfaces showed good signal peaks and reproducibility.