Herein, a novel copper-catalyzed reaction of tosylmethylisocyanide (TosMIC) with benzyl alcohols has been developed using tert-butyl hydroperoxide (TBHP) for the first time. The reaction involves the in-situ oxidation of benzyl alcohol to corresponding benzaldehyde, followed by sequential formal [3+2] cycloaddition/radical addition/ring oxidation reactions, and provides an efficient method for the construction of 4-(tert-butylperoxy)-5-aryloxazol-2(3H)-ones from readily available starting materials. Replacement of TBHP with H2O2 led to the production of 5-aryloxazol-2(5H)-ones in good yields. Graphic Tandem oxidative Van Leusen reaction: efficient three-component approach for the synthesis of 4-(tert-butylperoxy)-5-aryloxazol-2(3H)-ones and 5-phenyloxazol-2(5H)-one for the first time.