Adsorption and decomposition of tert-butylacetylacetate (tBAA) on Si(100) have been investigated using static secondary ion mass spectrometry and temperature-programmed desorption. At low doses, all tBAA molecules dissociate readily upon adsorption on the surface at temperatures as low as -160 degreesC. The dissociation may occur through tBAA bonding via the ester oxygen or the carbonyl group to the surface, The bond scission occurring at the tBuO-CO bond leads to the formation of surface tert-butoxide. Further dehydrogenation can take place to yield isobutene and surface hydroxyl species. Subsequent heating of the substrate causes the hydroxyl to decompose, and the resulting substoichiometric silicon oxide sublimes as SiO. The surface-induced bond scission also occurs at the OC-CCO bond of the tBAA diketo moiety to produce isobutene. In addition, the OC-CCO bond scission induced by tBAA surface bonding, mainly via its carboxylic keto oxygen, affords acetaldehyde radical, whereas that induced mainly via the aceto oxygen yields carbon dioxide and isopropenoxy species. An enol-keto conversion takes place when isopropenoxy species acquire surface hydrogen to yield acetone, even at low substrate temperature of less than -126 degreesC The aceto oxygen pathway dominates the cleavage of the OC-CCO bond. Increasing substrate temperature also causes the surface tert-butyl fragments to further react through different beta -hydride elimination pathways, forming isobutene, which is either in the gaseous state or bound to the surface in a di-sigma configuration.