In this work, the effect of a nucleating agent on the crystallization structure of an injection-molded bar of a polypropylene random copolymer (PPR) with sorbitol derivatives [1,2,3,4-dibenzylidene sorbitol (DBS)] has been studied. The results show that pure PPR forms a simple skin-core crystallization structure. However, PPR/DBS forms an interesting and complicated hierarchy crystallization structure: there is a transition layer between the skin layer and the core zone. In this transition layer, the crystallization structure consists of some perfect spherulites and many tiny crystallites. Further research suggests that the formation of the hierarchy crystallization structure depends on not only the content of the nucleating agent in the PPR matrix but also the mold temperature during the injection-molding processing. The crystallization behavior of PPR/ DBS during the cooling process has been characterized with polarization optical microscopy and differential scanning calorimetry. The results suggest that there are different mechanisms in the crystallization process of PPR/DBS. The formation of a three-dimensional DBS network under a certain condition might be the main reason for the complicated hierarchy crystallization structure. (C) 2007 Wiley Periodicals, Inc.