Fourier transform infrared (FTIR) transmission spectroscopy was used to monitor the decomposition of diethylsilane (DES) on high surface area porous silicon samples. The FTIR spectra revealed that DES dissociatively adsorbs on porous silicon to form and species. The infrared absorbances of the stretching vibrations at 2955‐2879 cm−1 and the stretching vibration at 2088 cm−1 were employed to monitor the decomposition of the surface species. As the silicon surface was annealed to 500–750 K, the species decomposed to produce gas phase ethylene and additional surface species. These reaction products were consistent with a β‐hydride elimination reaction. Above 700 K, the surface species decreased concurrently with the desorption of from the porous silicon surface. The uptake of surface species was also monitored at various adsorption temperatures to determine the optimal DES exposure temperatures for silicon deposition. Carbon contamination was minimal at DES adsorption temperatures below 640 K prior to desorption. Because the DES adsorption process is self‐limiting at temperatures below 640 K, DES may be a useful molecular precursor for the atomic layer epitaxy of silicon.