The van der Waals complex Li . . FH was formed in crossed beams and the transition state of the excited-state reaction, Li*(2p P-2)+HF --> LiF+H, was accessed by photoexcitation of this complex. The dynamics of the excited-state reaction were probed by varying the excitation wavelength over the range 570-970 nm while recording the photodepletion of the complex. The findings were interpreted using high-level ab initio calculations of the ground and lowest excited-state potential-energy surfaces.