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Ternary rare earth coordination chain transfer polymerization system of neodymium 2,5-dimethyl-2-ethylcaproate / diisobutyl aluminum hydride / dichlorodimethylsilane was used, and the ring opening polymerization of dicyclohexlactone 4,4ˊ- dioxane heptyl-7,7ˊ- dione (BOD) was successfully initiated, the star polybutadiene with polyester cross-linked core structure was prepared. The results showed that the weight average molecular weight of the star polymer increased gradually with the increase of the amount of BOD in the polymerization reaction. At the same time, due to the inconsistent number of arms of the star polymer, the molecular weight distribution became wider. In addition, the Mark-Houwink equation parameter α of star polybutadiene were obtained. It is significantly smaller than linear polymer, but agreed well with the α of traditional star polymer.