We have demonstrated a new application of our oxidizing reagent, a combination of NH₂OH·HCl and NaIO₄, in the first generalized regioselective 1,2-difunctionalization of olefins. It is a general method for the preparation of β-iodo-β′-hydroxy ethers, β-iodo ethers, β-iodohydrin, and β-iodo acetoxy compounds using different reaction media. The reactions are highly regioselective, always affording Markovnikov's type addition products. The methodology is also applicable for the easy access of terminal acetals. Molecular iodine-free synthesis, room temperature reaction conditions, high yields, use of less expensive reagents, mild reaction conditions, broad applicability of nucleophiles, and applicability for gram-scale synthesis are the notable advantages of this present protocol.