The Cu(OAc)2-catalyzed one-pot three-component cycloaddition of malonates, nitrosoarenes and alkenes is described. A wide range of isoxazolidines could be obtained in moderate to excellent yields via this method. Mechanistic investigations indicated that the key step in this catalytic system is the straightforward formation of nitrone intermediates through the Cu(OAc)2-catalyzed reaction of malonates with nitrosoarenes.