A heterogeneous catalyst containing MoO42- exchanged on layered double hydroxides (Mo-LDHs) is used to produce O-1(2) from H2O2, and with this dark O-1(2), unsaturated hydrocarbons are oxidized in allylic peroxides. The oxidation kinetics are studied in detail and are compared with the kinetics of oxidation by O-1(2), formed from H2O2 by a homogeneous catalyst. A model is proposed for the heterogeneously catalyzed O-1(2) generation and peroxide formation. The model divides the reaction suspension in two compartments: (1) the intralamellar and intragranular zones of the LDH catalyst; (2) the bulk solution. The 2-compartment model correctly predicts the oxidant efficiency and peroxide yield for a series of olefin peroxidation reactions. O-1(2) is generated at a high rate by the heterogeneous catalyst, but somewhat more O-1(2) is lost by quenching with the heterogeneous catalyst than using the homogeneous catalyst. Quenching occurs mainly as a result of collision with the LDH hydroxyl surface, as is evidenced by using LDH supports containing strong O-1(2) deactivators such as Ni2+. A total of 15 organic substrates were peroxidized on a preparative scale using the best Mo-LDH catalyst under optimal conditions.