The molecular weight of self-emulsifying amphiphilic epoxy sizing emulsions has a big effect on the carbon fibres and interfacial properties of their composites. Novel amphiphilic epoxy sizing emulsions with four different molecular weights (7500, 11,000, 15,000 and 17,000) were successfully prepared by a self-emulsifying method and applied to improve interfacial bonding between carbon fibres (CFs) and an epoxy resin (EP). The effect of molecular weight on the quality of emulsions, the sized CFs and the interfacial properties of the CF/EP composite system were studied. The results reveal that these novel sizing emulsions exhibited strong emulsifying ability and high processability. The most favourable wettability and adequate CF surface free energy were obtained by the emulsion with a molecular weight of 7500. Compared with unsized CFs, the monofilament fibre tensile performance was remarkably improved when increasing the shape parameter from 5.08 to 7.20. The interfacial sheer strength (IFSS) of the CF/EP composite was greatly increased by 96% with the emulsion of 7500. The enhanced interfacial adhesion benefits were attributed mainly from the enhanced charge interaction between CFs and the sizing layer as well as the compatibility and the mechanical interlock between the sizing layer and the epoxy matrix.