An extensive computational study has been carried out on different catalytic systems for cyclopropanation reactions based on copper. Most DFT schemes used present drawbacks that preclude the calculation of accurate absolute kinetic properties (energy barriers) of such systems, excepting the M05 and M06 suites of density functionals. On the other hand, there is a wide range of DFT methods capable of reproducing relative energy values, which can be easily translated into selectivities. Most of the theoretical levels used tend to overestimate activation barriers, allowing the location of the transition state (TS) on the potential-energy surface (PES) of the most reactive systems, which are probably artifacts of the method. However, after a thorough analysis of the calculated PES, and the origin of the energy differences obtained for the different alkene approaches in chiral systems, it is found that energy differences are almost constant over a wide range of geometries covering the reaction channel zone in which the true TS on the Gibbs free-energy surface (GFES) lies. Therefore, many computational schemes can still be used confidently to explain and predict enantioselectivities in these systems.