A highly active catalytic system for the carbonylation of meso- and terminal epoxides to β-lactones is described. The active catalyst, analogous to Coates’ catalyst, is generated in situ from commercially available (TPP)CrCl and Co2(CO)8. This practical system circumvents the preparation of air sensitive cobaltate salts, operates at low catalyst loadings, and allows the carbonylation of functionalized, sterically demanding and heterocyclic meso-epoxides