Direct collisionless multiphoton (MP) excitation of the triplet vibronic manifold of biacetyl is reported. Following a dye laser pulse which prepares some of the biacetyl molecules in the triplet metastable state, the system is irradiated by an intense 20 ns 9.6μ CO2 pulse. The CO2 radiation induces fast quenching of the phosphorescence emission from the 3Au excited molecules. It also induces an emission signal in the fluorescence spectral region of biacetyl. This signal is related to an inverse electronic relaxation (IER) from excited triplet vibronic levels into isoenergetic singlet 1Au vibronic levels. Analysis of the induced luminescence signals provides information on the collisionless MP prompted vibrational distribution. Excitation with 10.6μ CO2 pulses leads to the simultaneous MP pumping of both the ground and triplet manifolds. The generation of blue emission signals in this experiment bears a close resemblance to recent observations of prompt visible emission due to MP pumping of ground state molecules. General expressions for the emission intensities are derived with special emphasis on the specific features of MP vibrational distributions. The detectability of MP induced emission signals is discussed.