Characteristics of the single and double Ne van der Waals complexes of p-difluorobenzene (pDFB) have been explored with ultraviolet fluorescence excitation and dispersed fluorescence spectroscopy. Eight S-1-S-0 fluorescence excitation bands involving six ring modes of pDFB-Ne and two bands of pDFB-Ne-2 have been identified. Band assignments are confirmed by dispersed fluorescence from the pumped band. Shifts of the complex bands from the analogous monomer bands are generally 4 cm(-1) to the red for pDFB-Ne and 8 cm(-1) for pDFB-Ne-2. None of the observed ring modes is significantly perturbed by complexation in either the S-1 or S-0 states. The pDFB-Ne S-1 van der Waals binding energy D-0' less than or equal to 120 cm(-1) is inferred from fluorescence band assignments with D-0' -D-0" = 4 cm(-1). Vibrational predissociation of pDFB-Ne to produce the S-1 monomer is observed after pumping several levels, but the dissociation process is generally slow compared to fluorescence decay of the complex. Dissociation of the double complex pDFB-Ne-2 occurs from one level to produce S-1 pDFB-Ne in its zero point level. Comparisons are made with the relaxation dynamics of the S-1 complexes pDFB-Ar and pDFB-N-2. (C) 2004 American Institute of Physics.