The Rydberg atom time-of-flight method has been employed for velocity, angular and spin-orbit state-resolved detection of oxygen atoms, O(P-3(J)). The atoms were "tagged'' by double-resonance two-photon excitation to high-n Rydberg levels and subsequently field ionized at a detector. The method was characterized by studying a well-known system, the photodissociation of NO2 at 355 nm. From the O atom time-of-flight spectra, the NO vibrational distribution for different O(P-3(J)) levels was obtained, with NO (v = 1) rotational structure partially resolved. (C) 2003 American Institute of Physics.