Vanadium porphyrin complexes are naturally occuring substances found in crude oil and have been shown to have medicinal properties as well. Little is known on their activities with substrates; therefore, we decided to perform a detailed density functional theory study into the properties and reactivities of vanadium(IV)- and vanadium(V)-oxo complexes with a TPPCl8 or 2,3,7,8,12,13,17,18-octachloro-meso-tetraphenylporphyrinato ligand system. In particular, we investigated the reactivity of [VV(O)(TPPCl8)]+ and [VIV(O)(TPPCl8)] with cyclohexene in the presence of H2O2 or HCO4–. The work shows that vanadium(IV)-oxo and vanadium(V)-oxo are sluggish oxidants by themselves and react with olefins slowly. However, in the presence of hydrogen peroxide these metal-oxo species can be transformed into a side-on vanadium-peroxo complex, which reacts with substrates more efficiently. Particularly with anionic axial ligands, the side-on vanadium-peroxo and vanadium-oxo complexes produced epoxides from cyclohexene with small barier heights. In addition to olefin epoxidation, we investigated aliphatic hydroxylation mechanisms of the same oxidants and some oxidants show efficient and viable cyclohexene hydroxylation mechanisms. The work implies that vanadium-oxo and vanadium-peroxo complexes can react with double bonds through epoxidation, and under certain conditions also give hydroxylation, but the overall reactivity is highly dependent on the equatorial ligand, the local environment and the presence of anionic axial ligands.