Time-of-flight mass spectrometry (TOF-MS), resonance-enhanced multiphoton ionization (REMPI), and zero kinetic energy (ZEKE) photoelectron spectroscopy were employed to study the phenol-Kr and phenol-Xe van der Waals (vdW) complexes in their neutral excited (S I) and cationic ground (DO) state. For each complex, excitation and ionization energies and their red shifts relative to the corresponding data for bare phenol were determined. Inter- and intramolecular vibrational frequencies were recorded for the S, state of the neutral complex, which were used as intermediate resonances for the observation of vibrational modes of the cationic state. Possibilities of different structures, that is, above ring position of the rat-e gas atom and "hydrogenbonded"-like (HB) isomer, were investigated. Finally, the present results are compared to available data on similar systems, for example, phenol-Rg and other complexes of rare gas atoms with aromatic molecules.