A VUV (vacuum-UV) three-photon hot molecule reaction;is demonstrated in this study for gaseous triphenylmethane (TPM). A TPM radical was derived from vibrationally hot TPM, which sequentially absorbed the second and third photons within a laser pulse. In the condensed phase, TPM radical was formed by the deprotonation of a cation radical, which was formed by the two-photon ionization. The multiphoton reaction via a hot molecule is a special case which can produce a neutral radical directly. This study also shows that more than two high-energy photons (VUV) can be absorbed and accumulated as vibrational energy. It should be emphasized that an internal conversion is not a useless photophysical process, but a very interesting process for forming an important intermediate in multiphoton laser chemistry.