Copper-catalyzed alkene amino oxygenation reactions using O-acylhydroxylamines have been achieved for a rapid and modular access to diverse 1,2-amino oxygen-containing molecules. This transformation is applicable to the use of alcohols, carbonyls, oximes, and thio-carboxylic acids as nucleophiles on both terminal and internal alkenes. Mild reaction conditions tolerate a wide range of functional groups, including ether, ester, amide, carbamate, and halide. The reaction protocol allows for starting with free amines as the precursor of O-benzoylhydroxylamines to eliminate their isolation and purification, contributing to broader synthetic utilities. Mechanistic investigations reveal the amino oxygenation reactions may involve distinct pathways, depending on different oxygen nucleophiles.