A convenient method for β-bromo-formyloxylation of olefins with N, N-dibromobenzenesulfonamide and formic acid was developed. Cyclohexene, styrene, trans-β-methyl-styrene, and 1-hexene were made to react to give trans-2-brmocyclohexyl formate (I), 2-bormo-1-phenylethyl formate (II), erythro-2-bromo-1-phenylpropyl formate (III), and 1-bromo-2-hexyl fromate (IV).