A new type of hierarchical hemisphere-like CaCO3 (HSCC) was developed by a biomineralization method and incorporated into poly(p-dioxanone) (PPDO) by in situ ring opening polymerization (ROP) to develop the :Composites with comprehensive and good performances. The mechanical property, thermal stability, crystallization behavior, and degradation behavior of PPDO/HSCC composites were investigated. The tensile strength, the elongation at break, and the modulus of PPDO were enhanced simultaneously by the addition of HSCC, because of its good dispersion and interfacial adhesion with PPDO matrix. In addition, HSCC in composites also acted as a nucleating agent and enhanced the crystallinity of PPDO. The degradation rate of the PPDO/HSCC composites was enhanced with introducing 3 wt % HSCC, while 1 wt % HSCC did not change the degradation rate of PPDO. It was worth mentioning that, compared to PPDO, the pH value of incubation solution was more stable for PPDO/HSCC composites. Because HSCC could neutralized the acid residue, which illustrated the inflammation risk caused by the acid residue could be reduced. In particular, the good cell attachment and proliferation of both L929 and MG-63 cells was obtained for PPDO/HSCC with an HSCC amount of 3 wt %. The results indicated hierarchical HSCC played a very important role in improving the physical and biological properties of PPDO, which made PPDO/HSCC composites hold a promising application in bone tissue engineering material.