Reported here is a copper-catalyzed 1,2-methoxy methoxycarbonylation of alkenes by an unprecedented use of methyl formate as a source of both the methoxy and the methoxycarbonyl groups. This reaction transforms styrene and its derivatives into value-added b-methoxy alkanoates and cinnamates, as well as medicinally important five-membered heterocycles, such as functionalized tetrahydrofurans, g-lactones, and pyrrolidines. A ternary b-diketiminato-CuI-styrene complex, fully characterized by NMR spectroscopy and X-ray crystallographic analysis, is capable of catalyzing the same transformation. These findings suggest that pre-coordination of electron-rich alkenes to copper might play an important role in accelerating the addition of nucleophilic radicals to electronrich alkenes, and could have general implications in the design of novel radical-based transformations.