AbstractMINDO/3 and STO‐3G MO calculations including geometry optimization have been performed for nonlinear C6H+5structures. The phenyl cation5is the lowest energy compound on the surface, followed by the nonclassical pyramidal carbenic structure4. Other local minima include the bicyclic carbene6and the benzvalenyl cation7. Fairly good agreement between the results from both methods was obtained. The electronic structure of4is explained using orbital interaction diagrams which show the stabilization of the cyclopentadienyl cation by the apical carbon atom and the relation between4and pyramidal transition‐metal complexes. The electronic structure of6is related to that of the bicyclo[3.1.0]hexenyl cation12. Activation energies for rearrangement reactions on the energy surface show that4can probably be studied starting from benzvalene‐type precu