Hydrogenations have been dominated by transition metal catalysis, while the use of more abundant and inexpensive main group metal catalysts has remained a great challenge. Here, a bimetallic Li/Al dihydride was successfully applied to catalytic hydrogenations of imines. The catalyst [(DippBIAN)Al(μ-H)2Li(OEt2)2] was easily prepared from the 2e-reduced BIAN derivative and LiAlH4.