Na 3 O has been generated by reacting preformed sodium clusters with O 2 and N 2 O in a crossed beam pickup arrangement. This ''superalkali'' species was probed by photodepletion spectroscopy coupled with one-photon ionization mass spectroscopy to yield: ͑i͒ a first measure of visible/NIR region photodissociation cross sections showing several broad absorption features, ͑ii͒ a rough determination of the ground state dissociation energy (1.48Ϯ0.04 eV), as well as ͑iii͒ a remeasurement of the ionization potential (3.69Ϯ0.15 eV). The experimental investigations were supplemented by quantum chemical ab initio calculations employing coupled-cluster methods for ground and excited states of Na 3 O. Experiment and theory are in good agreement, allowing a tentative assignment of the Na 3 O depletion spectrum while providing further evidence for the computed D 3h ground state. Observed and calculated dipole-allowed electronic transitions are discussed in terms of the unusual electronic structure of this nominally one excess-electron species.