Ultrafast energy relaxation of Cr(acac)3 dissolved in tetrachloroethylene (TCE) is studied by time-resolved infrared (TRIR) spectroscopy by using electronic and vibrational excitation. After electronic excitation at 400 or 345 nm, the ground state recovers in two time scales: 15 ps (major pathway) and 800 ps (minor pathway), corresponding to fast electronic transition to the ground state and intermediate trapping on the long-lived (2)E state followed by intersystem crossing (ISC) to the ground state. The quantum yield for the fast recovery of the ground state depends on the excitation wavelength, being higher for 345 nm. Vibrational cooling (VC) occurs on the electronic excited states with a time constant of ∼7 ps and on the ground electronic state with a time constant of ∼12 ps. A kinetic model that explains the observed dynamics is presented. The key point of the model is that the ground-state recovery occurs via thermally activated back-intersystem-crossing (b-ISC) to the quartet manifold presumably via multiple curve crossings that are sampled while the system is vibrationally hot. This underlines the importance of vibrational cooling as a determining factor for the electronic relaxation chain. Vibrational excitation of the νC═C and νCO vibrations also revealed a subpicosecond (300-700 fs) intramolecular vibrational redistribution (IVR) process from the localized vibrational states to the bath of vibrational excitations.