Interests on carbon fiber-reinforced thermoplastic composites are growing rapidly, but the challenges with poor interfacial adhesion have slowed their adoption. In this work, a polyether sulfone (PES) emulsion sizing was prepared successfully for increased interfacial adhesion of carbon fiber/PES composites. To obtain a high-quality PES emulsion sizing, the key factor, emulsifier concentration, was studied by dynamic light scattering technique. The results demonstrated that the suitable weight ratio of PES to emulsifier was 8:3, and the resulting PES emulsion sizing had an average particle diameter of 117nm and Zeta potential of −52.6mV. After sizing, the surface oxygen-containing functional groups, free energy and wettability of carbon fibers increased significantly, which were advantageous to promote molecular-level contact between carbon fiber and PES. Finally, short beam shear tests were performed to evaluate the interfacial adhesion of carbon fiber/PES composites. The results indicated that PES emulsion sizing played a critical role for the enhanced interfacial adhesion in carbon fiber/PES composites, and a 26% increase of interlaminar shear strength was achieved, because of the improved fiber surface wettability and interfacial compatibility between carbon fiber and PES.