The vibrational predissociation (VP) dynamics of toluene-Ar and toluene-Ne complexes have been investigated using single vibronic level fluorescence spectroscopy. For several levels, comparison of the dispersed fluorescence spectra wit those from monomer levels permits the identification of the final monomer vibrational level. Pumping of the low-lying S-1 13(0)(1)/24(0)(1)/25(0)(1) or 37(0)(1) transitions in toluene-Ar, for example, gives rise to efficient VP leaving the resulting toluene monomer in its vibrationless S-1 state. By contrast, in the case of toluene-Ne, VP following 37(1) level pumping leaves the toluene molecule in an excited 16(1) level which is optically inaccessible from the ground state. (c) 2007 Elsevier B.V. All rights reserved.