Compared with the most stable crystalline form of isotactic polypropylene (alpha-iPP), beta-iPP shows superior impact strength and high temperature performance, though the mechanism of how the frustrated structure of beta-iPP is formed still remains unclear. In present work, the single crystal structure of a traditional beta-iPP nucleating agent, N, N '-dicyclohexylterephthalamide (DCHT), was obtained for the first time and correlated with the epitaxial crystallization of beta-iPP on the surface of DCHT crystal. The combination of synchrotron radiation X-ray microdiffraction and molecular chain packing model confirmed that a two dimensional match of chain-axis and inter-chain direction coexists between beta-iPP (110) plane and DCHT (001) plane. It was further found that an epitaxial model is helpful to understand the formation of the frustrated structure of 31 helices packing in beta-iPP. The molecular mechanics computation showed that as the (001) plane of DCHT is fixed, the packing mode of beta-iPP (110) plane on the substrate surface is more stable than that of alpha-iPP (010) plane. This work clarifies the epitaxial crystallization mechanism of beta-iPP on DCHT by employing both experimental and computational evidences. (C) 2017 Wiley Periodicals, Inc.