Oxo-rhenium compounds, such as perrhenate salts, have demonstrated preferable activity in catalyzing the deoxydehydration (DODH) reaction in the presence of reductants. Here, the first computational details of the reported DODH mechanisms are presented using the density functional theory (DFT) (M06/6-3111-G(d,p)/LANL2DZ) to investigate the conversion of a vicinal diol into the corresponding alkene by ReO4- as a catalyst. The DFT studies were carried out to evaluate the DODH mechanisms, from the energy point of view, for the conversion of phenyl-1,2-ethanediol to styrene by perrhenate anion in the presence of PPh3 as a reductant through a detailed comparison of two potential pathways including pathway A and pathway B. Pathway A includes the sequence of condensation of oxo-Re(VII) with diol before the reduction of Re(VII) to Re(V), whereas pathway B involves the reduction of oxo-Re(VII) to oxo-Re(V) before the condensation process. In pathway B, two basic routes (B1 and B2) are possible, which can take place through different reaction steps, including the extrusion of alkene from Re(V)-diolate in route B1, and the second reduction of the Re(V)-diolate by reductant and then the extrusion of alkene from the Re(III)-diolate intermediate in route B2. The intermediates and the Gibbs free energy changes, including Delta G degrees(g) and Delta G degrees(sol), have been calculated for alternative pathways (A and B) in the gas and solvent (chlorobenzene and methanol) phases and compared to each other. In addition, the transition states and the activation energy barriers for two pathways (A and B) in the gas phase and in chlorobenzene have been calculated. The key transition states include the nucleophilic attack of PPh3, on an Re=O bond, the dissociation of OPPh3 from the rhenium moiety, the transfer of an H atom of diol to the oxo ligand in an oxo-Re bond through the condensation step, and the extrusion of styrene from the Re-diolate complexes. The DFT results indicate that the DODH reaction is thermodynamically feasible through both pathways (A and B). However, the calculations reveal that the perrhenate-catalyzed DODH reaction through pathway A has the lowest overall activation barrier energy among the DODH mechanism routes.