A porous MgAl2O4 spinel-supported Mn3O4 catalyst, which is an efficient and robust catalyst for polyethylene terephthalate (PET) glycolysis, was synthesized from MgAl-layered double hydroxide (LDH) as a template via thermal and chemical treatment, followed by Mn oxide loading. A mesoporous structure in the MgAl2O4 spinel provided a high surface area (278 m2/g) and defects in which Mn3O4 was highly dispersed and strongly stabilized by the substitution of Al3+ and incorporation of Mn cation into the defects. The strong interaction of Mn oxide and the porous MgAl2O4 spinel support led to a dramatic increase of moderate acidic and basic properties, and to high resistance for Mn leaching during glycolysis. Using the Mn3O4/p-spMgAl800 catalyst, a yield of bis(2-hydroxyethyl) terephthalate > 95 % was achieved within 3 h at 190 ℃. Despite eleven recycling times with regeneration, the catalytic activity remained without significant deactivation and was completely recovered after thermal regeneration at 500 ℃.