Binary complexes of OH X 2Π and H2/D2 have been stabilized in the entrance valley to the hydrogen abstraction reaction and identified in the OH A 2Σ+–X 2Π 0–0 spectra region. Nearly all of the intermolecular vibrational levels supported by the OH A 2Σ+ (v′=0)+H2/D2 potential energy surface have been observed in fluorescence depletion experiments. Rapid electronic quenching precludes the observation of OH–H2/D2 prepared in these levels by laser-induced fluorescence. A sharp onset of laser-induced fluorescence occurs at the OH A 2Σ+ (v′=0)+H2/D2 dissociation limit. The binding energies for OH–H2/D2 in the ground state correlating with OH X 2Π (v″=0)+H2/D2 have been determined to be 54 cm−1 and more than 66 cm−1, respectively. The OH A 2Σ+ (v′=0)+H2/D2 excited state is found to be at least 577 cm−1 (H2) and 639 cm−1 (D2) more strongly bound than the ground state. The positions of observed features are compared with the corresponding intermolecular levels observed by laser-induced fluorescence in the OH A–X 1–0 region as well as theoretical predictions of the transition energies based on ab initio potentials for the ground and excited electronic states. The OH–H2/D2 intermolecular levels correlating with OH A 2Σ+ (v′=0)+H2/D2 have lifetimes of 3.2–4.5 ps, deduced from homogeneous linewidths, due to quenching and/or chemical reaction.