A new concept of room temperature selective oxidation of olefins, alkyl substituted benzenes and alkanes by electron transfer from the hydrocarbon to the oxygen molecule induced by irradiation with visible light is shown. The hydrocarbon radical cation-O-2 charge-transfer pair is generated inside the cavities of alkali or alkaline-earth ion-exchanged zeolites, in which the large electrostatic field stabilizes the highly polar charge-transfer states of hydrocarbon-O-2 collisional pair and allows to control the pathways of further transformation. High selectivities to useful products are obtained using this approach.