Oxorhenium(V) complexes of the general formula [ReOCl2(PPh3)(L)] (2a-c) and [ReOCl(L)2] (3a-c) with L being monoanionic, bidentate phenolate-pyrazole ligands 1a-c that bear substituents with various electronic features on the phenol ring (1a Br, 1b NO2, 1c OMe) were prepared. The compounds are stable toward moisture and air, allowing them to be handled in a normal lab atmosphere. All complexes were fully characterized by spectroscopic means and, in the case of 2b, 2c, 3b, and 3c, also by single-crystal X-ray diffraction analyses. Electrochemical investigations by cyclic voltammetry of complexes 3a-c showed a shift to more positive potentials for the Re(V)/Re(VI) redox couple in the order of 3b > 3a > 3c (R = NO2 > Br > OMe), reflecting the higher electrophilic character of the Re atom caused by the ligands 1a-c. Complexes 2a-c and 3a-c display excellent catalytic activity in the epoxidation of cyclooctene, where all six complexes give quantitative conversions to the epoxide within 3 h if tert-butylhydroperoxide (TBHP) is employed as oxidant. Moreover, they represent rare examples of oxorhenium(V) catalysts capable of using the green oxidant hydrogen peroxide, leading to high yields up to 74%. Also, green solvents such as diethylcarbonate can be used successfully in epoxidation reactions, albeit resulting in lower yields (up to 30%).