Adsorption of aniline and pyridine on the H- and HO-terminated Si(100) surfaces has been investigated by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and density functional theory (DFT) calculations. Surface functionalization reactions were conducted under solution-chemistry conditions and an inert atmosphere, and show that adsorption proceeds very differently for aniline and pyridine on H-, and HO-Si(100) surfaces. On hydrogen-terminated silicon surfaces, aniline forms