Gamma-Butyrolactone (GBL) is recovered from a mixture containing GBL and other heavy organics by a process of azeotropic distillation in the presence of a C8-C 10 hydrocarbon as an azeotroping agent, wherein an azeotrope of GBL and the hydrocarbon is obtained as a distillate, which forms immiscible GBL-rich and hydrocarbon-rich phases, and the hydrocarbon-rich phase is decanted or isolated from the GBL-rich phase. By this process GBL can be efficiently separated from a large proportion of various compounds having boiling points close to that of GBL, e.g., the methyl-&ggr;-butyrolactones (MeGBL's).