Calculations are reported at the MP2/6-311++G(2df,2pd) level of theory on the reaction of K atoms with CH3Cl, with different orientations of the CH3Cl molecule with respect to the incoming K atom. As was found for the CH3CN + K system, approach along a minimum energy pathway does not lead to electron transfer at the energies of the reported experiments. Stretching of the C-Cl bond of CH3Cl facilitates electron transfer. The barrier to electron transfer is less for approach from the Cl end of CH3Cl. Unlike the case for the CH3CN + K system the barrier to formation of CH2Cl- + H is greater than that to form CH3Cl-or CH3 + Cl-.