AbstractIn this paper we present the three dimensional EHMO crystal orbital calculations for crystalline Li2CsC60, Na2CsC60, K2CsC60and Rb2CsC60. For all these four dopants with a fcc structure, our calculated band structures and density of state unequivocally suggest a metallic conducting phase with each a set of three half‐filled band across the Fermi level which is just located close to a peak of density of state. A monotonic relationship is found between our calculated Fermi‐level density of stateN E fand experimental transition temperatureTcwhich is in excellent agreement with some theoretical studies and experimental results. With our other calculation results, such as the overlap populations between A (where A represents an alkali‐metal) and C60molecules, net atomic and orbital charges, crystal orbital vectors and various projected DOS, we could probably shed some light on the mechanism of the superconductivity for this new marvelous kind of materials from a chemical poin