Vibrational energy transfer within the A 2Σ+ state of OH and OD has been studied. A frequency doubled tunable dye laser excites individual N′, J′ levels in v′=1 or 2, and the intensities of rotationally resolved fluorescence emitted in the presence of collision partners (He, Ar, H2, D2, and N2) furnished state‐to‐state transfer rates. It is found that the transfer rates are strongly dependent on initial rotational level (decreasing as Ni increases), that the final rotational state distributions are near thermal but hot, that isoenergetic transfer is small, and that the magnitudes for transfer 1→0, 2→1, and 2→0 are all similar. The rates themselves are large; for example, with N2, k1→0 (Ni=3) =1.7×10−10 cm3 sec−1. The results, taken together, are supportive of a long‐lived collision in which anisotropic attractive forces are of importance in the dynamics of the entrance channel.