Eight transition structures for the epoxidation of the chiral allylic alcohol (Z)-3-methyl-3-penten-2-ol (1) with peroxyformic acid have been computed by the B3LYP density functional method with 6-31G(d) and 6-31G(d,p) basis sets. The four lowest-energy transition structures and their respective pre-reaction clusters were fully re-optimized by employing 6-311+G(d,p) and correlation-consistent polarized valence triple-zeta cc-pZTV basis sets. The relative energies of the transition structures were found to be highly sensitive to the basis set applied. The transition state for threo product formation, anti-(2S,3R,4S)-TS-3f, with the lowest total energy (at B3LYP/611+G(d,p) and B3LYP/AUG-cc-pZTV) of all the TSs examined, has a planar peracid moiety and is a precursor for the 1,4 migration of the peracid hydrogen atom Ha to the peroxy oxygen atom O4. The use of different basis sets does not affect markedly the geometry of the anti-(2S,3R,4S)-TS-3f transition structure. The transition state for erythro epoxidation, syn-(2R,3R,4S)-TS-3a, is 0.9 kcal/mol higher in energy and possesses a nonplanar peracid approaching the C=C bond in a manner intermediate between spiro and planar. The relative energy and nonplanarity of this syn transition structure is highly sensitive to the basis set applied. With the smaller basis set, 6-31G(d,p), it is actually the lowest-energy TS and the peracid moiety is significantly skewed. The contribution of the four lowest energy transition stuctures 3a, 3b, 3e, and 3f to the threo/erythro product ratio has been assessed through an extended Curtin-Hammet principle analysis of this multi-transition state reaction. It has been found that this approach agrees well with the experimental threo/erythro product ratio, in particular when the corrections for a solvent effect are made within the self-consistent isodensity polarized continuum model (SCI-PCM).