The [3,2]- and the [1,2]-phosphatoxy rearrangements have been studied in the 2-(phosphatoxy)ethyl radical, the 2-(dimethylphosphatoxy)ethyl radical, and the 2-(phosphatoxy)propyl radical with the Becke3LYP/6-31G(d) density functional method. Barriers have also been calculated through single-point energy calculations at the B3LYP/6-311+G(d,p), PMP2/6-31+G(d,p), and, in part, QCISD/6-31G(d) levels of theory. In contrast to acyloxy rearrangements in otherwise identical systems, the [1,2]-shift pathway is slightly preferred in phosphatoxy rearrangements. The degree of charge separation is much more significant in the [3,2]- than the [1,2]-shift pathway. Barriers for phosphatoxy and dimethylphosphatoxy shifts are rather similar for both pathways. Introduction of a methyl group adjacent to the radical center lowers the barrier quite significantly. The effect is larger for the [1,2]- than for the [3,2]-shift. Inspection of the charge and spin density distributions indicates that this effect is composed of steric as well as polar contributions. On the basis of these results, the experimentally found ratio of [1,2]- to [3,2]-phosphatoxy rearrangements should be strongly dependent on solvent polarity as well as substrate substitution pattern. The syn-1,3-elimination of phosphate has been described as a novel reaction type. The barrier for this process is significantly lower than for syn-1,2-elimination of phosphate from closed shell substrates, but somewhat above the barriers for 1,2-phosphatoxy rearrangements.