Dehydrogenation and C-C bond cleavage of 1-butyne by the excited states of La and Ce atoms are investigated in laser-ablation metal molecular beams. The excited states of the metal atoms are prepared by resonant excitation, detected by resonant two-photon ionization spectroscopy, and the reaction products are monitored by photoionization time-of-flight mass spectrometry. The reactivities of La* [5d(F)6p (G°)] and Ce* [4f5d(F°)6s6p(P°) (H)] excited states are observed to be higher than those of the initial states of the corresponding metal atoms. The higher reactivities of the excited states are attributed to their higher energies and favorable electron configurations to form two covalent bonds of the metal-insertion intermediates. Although both excited La and Ce atoms show increased reactivities, the enhancement for Ce is much more pronounced than that of La, which cannot be explained by electron configurations alone. The larger reactivity enhancement from the initial states to the excited state of the Ce atom than that of La is due to the longer lifetime of the Ce excited state.