Co catalysts, obtained from a layered double Co-Zn-Al hydroxide, are highly active and stable towards the hydrogenolysis of glycerol to 1,2-propanediol (1,2-PDO) in aqueous media. The Co-673 catalyst, containing a CoO species, provided a glycerol conversion of 67.7% and a 1,2-PDO selectivity of 50.5%. The Co-873 catalyst comprising 16 nm Co nanoparticles gave a glycerol conversion of 70.6% and a 1,2-PDO selectivity of 57.8%. It was revealed that the CoO species in the Co-673 catalyst was readily converted to 50 nm Co particles under the glycerol hydrogenolysis conditions. The Co catalysts maintained a stable size and phase in recycling tests.