The transition structures for the ene reactions of cyclopropene with ethylene, propene, and cyclopropene have been located with ab initio molecular orbital calculations and the 6-31G* basis set and by DFT calculations with the Becke3LYP functional and the 6-31G* basis set. Several of the transition structures have also been located with CASSCF calculations. Energies of all stationary points were also evaluated with second-order Moller-Plesset theory using the RHF/6-31G* optimized geometry. The geometries of each transition structure and the energetics of each reaction are discussed and compared to the ene reaction of propene with ethylene. Calculations show that the cyclopropene ene reactions have much lower activation barriers than the propene-ethylene ene reaction, in agreement with experimental results, The transition structures have varying degrees of asynchronicity. The stabilities of the possible radical intermediates for each reaction are reflected in the geometries of the transition structures, The relief of strain in a cyclopropene, when acting as the enophile, accounts for the energetic differences in these reactions. The endo transition structure. for the dimerization is lower in energy than the exo transition structure by 2.7 kcal/mol at the Becke3LYP/6-31G* + ZPE level of theory. Secondary orbital overlap of a CH bond of the enophile with the pi-system at the central carbon of the ene is proposed to account for the preference for the endo transition structure, Barely stable diradical intermediates have been found for both endo and exo cyclopropene dimerization reactions, but it is likely that they are artifacts of the current level of theory.