The effect of post adsorbed atomic hydrogen on the adsorption, desorption, and decomposition of ethylene on Si(100)-(2×l) has been studied using high-resolution electron energy loss spectroscopy (HREELS), temperature programmed desorption (TPD), and low-energy electron diffraction (LEED). Exposures to atomic hydrogen of more than 1015 atoms/cm2 convert the initial (2×l) reconstruction of sp3-hybridized, di-σ bonded ethylene to a (l×l) structure. Furthermore, after post exposure to atomic hydrogen, the thermal desorption peak of molecular ethylene is shifted up by approximately 100 K and reduced in intensity. HREEL spectra for deuterated ethylene show the formation of a C-H bond after exposure to atomic hydrogen, whereas the C-C bond remains intact. We explain our data by an atomic hydrogen-driven conversion of the di-σ bonded ethylene to a mono-σ bonded surface ethyl. Thermal activation after post exposure to atomic hydrogen leads to decomposition of about 60% of the initial ethylene in contrast to the observed molecular desorption in the absence of hydrogen.