In past studies, we have observed copious emissions of ionic and atomic Zn from single-crystal ZnO accompanying irradiation of single-crystal ZnO with 193-nm excimer laser irradiation at fluences below the onset of optical breakdown. The Zn+ and ground state Zn° are studied using time-of-flight techniques and are mass selected using a quadrupole mass spectrometer. Simultaneously, we have observed emitted particles that are detectable with a Channeltron electron multiplier but cannot be mass selected. It is a reasonable hypothesis that these particles correspond to a neutral atom or molecule in highly excited long lived states. We provide strong evidence that they correspond to high lying Rydberg states of atomic Zn. We propose a production mechanism involving laser excitation via a two photon resonance excitation of Zn°.