The potential energy hypersurface for H2P(OH)2 has been explored at correlated levels. Seven local minima and 29 different stereopermutational transition states interconnecting them were located. The transition states correspond to internal rotation, pseudorotation, double pseudorotation, and pseudoinversion. The stereochemical consequences of these processes are analyzed in detail as is the nature of the singly occupied molecular orbital throughout. Geometric and natural bond orbital analyses indicate the importance of hyperconjugative interactions through phosphorus in stabilizing various kinds of stationary points. The latter effect is maximized for the interaction of equatorial substituents in the trigonal-bipyramidal phosphoranyl minima. Comparison to closed shell phosphoranes and monohydroxy- and other phosphoranyl radicals is provided. Dihydroxyphosphoranyl is predicted to possibly be stable to homolytic decomposition under suitable conditions and calculated electron spin resonance and infrared spectral data are provided.