Several chiral salen- and salan-type ligands and their vanadium complexes were prepared, characterized, and used as catalysts in the oxidation of styrene, cyclohexene, cumene, and thioanisole with H2O2. Overall, the V−salan complexes show slightly higher activity for alkene oxidation and significantly higher activity and enantioselectivity for sulfoxidation than their parent V−salen complexes. Mechanisms for the alkene oxidation are discussed, including the use of DFT for the comparison of several alternative mechanisms for epoxidation.