Per-2,3-acetyl-b-cyclodextrin is first synthesized by selective modification and used as core molecule for preparing a star-shaped macromolecular antioxidant (b-CD-DBHMP) via a twostep method. b-CD-DBHMP is characterized by 1 H-NMR, MALDI-TOF MS, and TGA. The performance of b-CD-DBHMP as antioxidant for natural rubber is determined by OIT and accelerated thermal aging test, and its extraction resistance is also investigated. The results show that b-CD-DBHMP with a Mn of 4.03 Â 10 3 g Á mol À1 is successfully obtained, and it possesses high thermal stability with an initial weight loss temperature of 290 8C. Moreover, b-CD-DBHMP is superior to DBHMP for the stabilization of NR against thermal oxidation, and exhibits better extraction resistance. Its possible antioxidative mechanism is also discussed.