The goal of this research is to improve poor network structure of polychloroprene rubber (CR)/epoxidized natural rubber (ENR) self-crosslinking blends, which could substitute traditional vulcanizates in some application area. Carbon black (CB)-CR/ENR blends were prepared by reacting CR with ENR in the presence of CB. The structure of CR/ENR blends was characterized by attenuated total-reflectance Fourier transform infrared spectroscopy (FTIR-ATR). The effect of CB loading on curing characterization and mechanical properties of CR/ENR blends was investigated, and the interaction among CR, ENR, and CB was studied using differential scanning calorimetry. The effect of CB loading on the Payne effect of CR/ENR was investigated using rubber process analyzer. Scanning electron microscope was used to characterize the morphology of CB-CR/ENR blends. The results showed that CR/ENR blends were obtained by the ring-opening reaction of epoxy groups in ENR and chlorine groups in CR. Mechanical properties of CR/ENR blends increased with the increase of CB loading. The Payne effect of CR/ENR became more remarkable with increasing CB loading. Morphology study indicated that interfacial compatibility between CR and ENR increased with the increase of CB loading because CB could strengthen the self-crosslinking network structure of CR/ENR blends. The promoting effect of CB on selfcrosslinking reaction was verified by the assessment of crosslink density. POLYM. COMPOS., 00:000-000, 2015.