We investigated herein the reactions of (Me3tacn)FeCln (1a: n = 3, 1b: n = 2) with common aluminum hydride reagents and a bulky dihydridoaluminate {Li(ether)2}{Al(OC6H3-2,6-(t)Bu2)}(μ-H)2, which yielded the diamagnetic hydrido complexes 2-4 containing Fe(II) and Al(III). In particular, the use of divalent 1b afforded excellent isolated yields. The structures of 2-4 were determined using spectroscopic and crystallographic analyses. The crystal structures showed distorted octahedral Fe centers and fairly short Fe-Al distances [2.19-2.24 Å]. The structures of cation moiety 2 and neutral complex 4 were further probed using DFT calculations, which indicated a stable low-spin Fe(II) state and strongly electron-donating nature of the (Me3tacn)FeH3 fragment toward the Al(III) center.