Selective oxidation of olefins to α,β-unsaturated ketones under mild reaction conditions have attracted considerable interest, since α,β-unsaturated ketones can serve to be synthetic precursors for various downstream chemical products. The major challenges inherently with this chemical oxidation are chem-, regio-selectivity as well as environmental concerns, i.e. catalyst recycle, safety and cost. Using atmospheric oxygen as an environmental friendly oxidant, we found that a metal-organic framework (MOF) constructed with Mn and tetrazolate ligand (CPF-5) showed good activity and selectivity for the allylic oxidation of olefins to α,β-unsaturated ketones. Under the optimized condition, we could achieve 98% conversion of cyclohexene and 87% selectivity toward cyclohexanone. The combination of a substoichiometric amount of TBHP (tert-butylhydroperoxide) and oxygen not only provides a cost effective oxidation system but significantly enhances the selectivity to α,β-unsaturated ketones, outperforming most reported oxidation methods. This catalytic system is heterogeneous in nature, and CPF-5 could be reused at least five times without a significant decrease in its catalytic activity and selectivity.