Ultrafast decay dynamics of the excited state in the thin films of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) have been directly observed by using fs time-resolved two-photon photoelectron spectroscopy. The lifetimes were measured up to the excess energy of 2 eV above the S-1 state. The highly excited state presumably S-2 decays with tau = 70 +/- 2 fs and S-1 with tau = 360 +/- 12 fs. The extremely short lifetimes indicate that those excited states undergo very fast non-radiative decay, which is consistent with low fluorescence quantum yields in the S-1 manifold. (C) 2003 Elsevier B.V. All rights reserved.