New data on the high resolution spectra of vibronic bands of the aniline-neon van der Waals complex with excess vibrational energy up to 1000 cm(-1) above the S-1 origin have been obtained. The rotationally resolved structure of the 12(0)(1) and 6a(0)(2) bands of both Ne-20-aniline and Ne-22-aniline isotopomers reveal: (1) a dynamical contribution to the linewidth of the molecular eigenstates, (2) the existence of an accidental perturbation responsible for a local increase of the relaxation rate. The results are interpreted in terms of the competition between intramolecular vibrational redistribution and direct vibrational pre-dissociation processes. (C) 2004 Elsevier B.V. All rights reserved.