The combustion mechanism of [AlCp*](4) (Cp* = pentamethylcyclopentadienyl), a ligated aluminum(I) cluster, was studied by a combination of experimental and theoretical methods. Two complementary experimental methods, temperature-programmed reaction and T-jump time-of-flight mass spectrometry, were used to investigate the decomposition behaviors of [AlCp*](4) in both anaerobic and oxidative environments, revealing AlCp* and Al2OCp* to be the major decomposition products. The observed product distribution and reaction pathways are consistent with the prediction from molecular dynamics simulations and static density functional theory calculations. These studies demonstrated that experiment and theory can indeed serve as complementary and predictive means to study the combustion behaviors of ligated aluminum clusters and may help in engineering stable compounds as candidates for rocket propellants.