The epoxidation of 1-octene and propene with hydrogen peroxide is performed using micellar catalysis. Linear terminal alkenes have successfully been epoxidized with a homogeneous catalyst solubilized in an aqueous micellar solution. The best micellar system, in terms of reactivity and activity, consists of a homogeneous porphyrin catalyst, Mn(TDCPP)Cl, solubilized in Triton X-100 micelles. The aggregation behavior of Triton X-100 micelles with and without different epoxidation catalysts has been studied. For the epoxidation of 1-octene with the Mn(TDCPP)Cl-Triton X-100 system, a conversion of about 25% with a selectivity toward octene oxide in excess of 97% was obtained after 30 min. The cocatalyst used was imidazole. The initial turnover frequency was 250 h(-1). The Mn(TDCPP)Cl-Triton X-100 system showed excellent stability, and virtually no deactivation of the porphyrin catalyst was observed. The same epoxidation reaction carried out in a mixture of dichloromethane and CH3CN had an initial turnover frequency of 392 h(-1), and the selectivity toward octene oxide was 94%.