Mass-analyzed threshold ionization spectroscopy (MATT) was used or a detailed investigation of the dissociation process of a fluorobenzene . Ar complex. The threshold ion spectra were recorded for the fluorobenzene monomer and the fluorobenzene . Ar complex by exciting the chromophore via different vibrational states of the S-1. The ion state spectra of the (fluorobenzene . Ar)(+) cation exhibit significant progressions of the van der Waals bending mode b(x), which indicates a significant structural change of the complex upon ionization. The disappearance of the threshold ion signal for a certain excess energy in the complex (fluorobenzene . Ar)(+) and the simultaneous appearance of the missing bands in the spectra of the fragment ion give an upper limit for the dissociation energy of the complex in the cationic state. In addition, one feature observed in the fragment ion spectrum of the complex recorded via exciting the S(1)6b(1) state reveals the relatively fast predissociation (<4 ns) of the complex, if the vibrational energy in the S-1 state exceeds the binding energy D-1 (D-1<302 cm(-1)).