A comprehensive ab initio study of the adsorption of benzene on the silicon(100) surface is presented. Five potential candidates ([2+2] adduct, [4+2] adduct, two tetra-σ-bonded structures, and one radical-like structure) for the reaction product are examined to determine the lowest energy adsorption configuration. A [4+2] butterfly structure is determined to be the global minimum (−29.0 kcal/mol), although one of the two tetra-σ-bonded structures (−26.7 kcal/mol) is similar in energy to it. Multireference perturbation theory suggests that the [4+2] addition mechanism of benzene on Si(100) is very similar to the usual Diels−Alder reaction (i.e., small or zero activation barrier), even though benzene adsorption entails the loss of benzene aromaticity during the reaction. On the other hand, the [2+2] cycloaddition mechanism is shown to require a relatively high activation barrier (17.8 kcal/mol), in which the initial step is to form a (relatively strongly bound) van der Waals complex (−8.9 kcal/mol). However, the net activation barrier relative to reactants is only 8.9 kcal/mol. Careful examination of the interconversion reactions among the reaction products indicates that the two tetra-σ-bonded structures (that are energetically comparable to the [4+2] product) can be derived from the [2+2] adduct with activation barriers of 15.5 and 21.4 kcal/mol. However, unlike the previous theoretical predictions, it is found that the conversion of the [4+2] product to the tetra-σ-bonded structures entails huge barriers (>37.0 kcal/mol) and is unlikely to occur. This suggests that the [4+2] product is not only thermodynamically the most stable configuration (lowest energy product) but also kinetically very stable (large barriers with respect to the isomerization to other products).