Reaction of an Al‐centered anion with toluene proceeded to form C−H cleaved product with a perfect meta‐selectivity and a relatively small kinetic isotope effect (KIE, kH/kD=1.51). DFT calculations suggested a two‐step reaction mechanism and electronically controlled meta‐selectivity arising from the electron‐donating methyl group. The reaction with other mono‐substituted arenes was also investigated. Reaction of an Al‐centered anion with toluene proceeded to form C−H cleaved product with a perfect meta‐selectivity and a relatively small kinetic isotope effect (KIE, kH/kD=1.51). DFT calculations suggested a two‐step reaction mechanism and electronically controlled meta‐selectivity arising from the electron‐donating methyl group. The reaction with other mono‐substituted arenes was also investigated.