Photoionization of the OH and OD radicals, produced from the H+NO2 and D+NO2 reactions, has been studied in the gas phase in the photon energy region 13.0-17.0 eV using constant ionic state (CIS) and photoelectron spectroscopy (PES) employing synchrotron radiation. Structure in the CIS spectra, recorded for the first and second photoelectron bands, has been assigned to excitation to (a (1)Delta,3d) and (A (3)Pi,3d) Rydberg states. A comparison of vibrationally specific OH and OD CIS spectra, and photoelectron spectra recorded at resonant wavelengths, has allowed a more complete assignment of structure observed in earlier photoionization mass spectrometric measurements These assignments have been supported by the results of Franck-Condon calculations. The CIS spectra have been shown to be dominated by structure arising from excitation from the outermost valence molecular orbitals of OH [the nonbonding 1 pi(O 2p) orbital and the bonding 3 sigma orbital] to O nd Rydberg orbitals. Photoelectron spectra recorded for the first bands of OH and OD at resonant photon energies have allowed more extensive vibrational structure to be obtained than has previously been recorded by PES experiments performed with inert gas discharge photon sources.