Commercial carbon fiber (CF) sizing agent is generally characterized by poor temperature resistance and incompatibility with polyamide resin, which adversely affects the interfacial properties of CF/polyamide composites. In this paper, we take advantage of the fact that polyamide 6 (PA6) can be synthesized in-situ by anion ring-opening polymerization of caprolactam (CPL), introduced CPL precursor onto the CF surface, and initiated the polymerization to generate PA6 coating to modify CF. By changing the concentration of precursor solution, the amount of PA6 on the CF surface was effectively regulated, and the modified CF coated completely and uniformly can be obtained. The results show that PCF-20 (CF treated with 20wt% precursor solution) reinforced polyamide composites have the best interfacial properties. Compared with the desized CF/PA6 composites, the interfacial shear strength (IFSS) and interlaminar shear strength (ILSS) of PCF-20/PA6 composites increased by 50.79% and 13.49%, respectively. The interface image illustrated that the high interfacial wettability of PA6 coating on CF surface results in mechanical mesh between fiber and resin, which is the main reason for the enhancement of composites interfacial properties. Therefore, the in-situ synthesis of PA6 coating to modify CF is an effective method to improve the interface properties of CF/polyamide composites.