Laser desorption of aniline-d7 from a single-crystal surface (0001) of sapphire (Al2O3) at a heating rate on the order of 10(8) K/s was studied usin,g pulsed infrared laser radiation for desorption and resonance enhanced multiphoton ionization (REMPI) for detection of the desorbed aniline molecules. On the basis of single-vibronic-level fluorescence (SVLF) spectra we unambigiously assign the 10b transition. REMPI spectroscopy provides vibrational temperatures and therefore describes the internal energy distribution, whereas the time-of-flight (TOF) profiles provide translational temperatures. All results are consistent with a thermal mechanism for desorption, i.e., pulsed heating of the sapphire surface on the nanosecond time scale leads to thermal desorption and rapid thermalization of the escaping molecules.