Electrocarboxylation of the C(sp3)-O bond in 1,3-oxazolidin-2-ones with CO2 to achieve β-amino acids is developed. The C-O bond in substrates can be selectively cleaved via the single electron transfer on the surface of a cathode or through a CO2• - intermediate under additive-free conditions. A great diversity of β-amino acids can be obtained in a moderate to excellent yield and readily converted to various biologically active compounds.