The accuracy of three popular DFr methods (hybrid, gradient-corrected, and local) has been evaluated on the HF-assisted addition of HF to ethylene. The possibility of forming trimolecular (two HF and one ethylene) and dimolecular (one HF and one ethylene) complexes and transition state structures during the transformation of HF and ethylene in fluoroethane is discussed. An energetically favorable pathway was selected on the basis of the computed potential energy surface for these two reactions.