The meta regioselectivity of the nucleophilic addition to methoxy-substituted arene-Cr(CO)₃ complexes has been investigated by theoretical methods using density functional calculations employing the hybrid-DFT approach Becke3LYP and a flexible all-electron basis set. By calculating the relative energies and conformational preferences of the competing reactive intermediates (regioisomeric primary addition products) it was, among other things, demonstrated that the preferred reaction pathway proceeds ia the most stable intermediate. Based on the theoretical results a refined mechanistic picture for a synthetically important metallorganic process was derived.