We report an original alkane elimination approach, entailing the protonolysis of triisobutylaluminum by the acidic hydrides from Cp*IrH4. This strategy allows access to a series of well-defined tri- and tetranuclear iridium aluminum polyhydride clusters, depending on the stoichiometry: Cp*IrH3Al­(iBu)22 (1), Cp*IrH2Al­(iBu)2 (2), (Cp*IrH3)2Al­(iBu) (3), and (Cp*IrH3)3Al (4). Contrary to most transition-metal aluminohydride complexes, which can be considered as AlH x+3x– aluminates and LnM+ moieties, the situation here is reversed: These complexes have original structures that are best described as Cp*IrH x n− iridate units surrounding cationic Al­(III) fragments. This is corroborated by reactivity studies, which show that the hydrides are always retained at the iridium sites and that the Cp*IrH3− moieties are labile and can be transmetalated to yield potassium (KIrCp*H3, 8) or silver ((AgIrCp*H3 n , 10) derivatives of potential synthetic interest. DFT calculations show that the bonding situation can vary in these systems, from 3-center 2-electron hydride-bridged Lewis adducts of the form Ir–H⇀Al to direct polarized metal–metal interaction from donation of d-electrons of Ir to the Al metal, and both types of interactions take place to some extent in each of these clusters.