Several low oxidation state aluminum-containing cluster anions, LAlH⁻ and LAl_n⁻ (n = 2–4, L = N[Si(Me)₃]₂), were produced via reactions between aluminum hydride cluster anions, Al_xH_y⁻, and hexamethyldisilazane (HMDS). These clusters were characterized by mass spectrometry, anion photoelectron spectroscopy, and density functional theory (DFT) based calculations. Agreement between the experimental and theoretical vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) validated the computed geometrical structures. Reactions between aluminum hydride cluster anions and ligands promise to be a new synthetic scheme for low oxidation state, ligated aluminum clusters.