Carbon fiber/phenolic resin composites were reinforced by the carbon fiber sized with the polymer films of phenol,m-phenylenediamine or acrylic acid,which was electropolymerized by cyclic voltammetry or chronopotentiometry. The contact angles of the sized carbon fibers with deionized water and diiodomethane were measured by the wicking method based on the modified Washburn equation,to show the effects of the different electropolymer film on the surface free energy of the carbon fiber after sizing by the electropolymerization. Compared with the unsized carbon fiber,which has 85.6°of contact angle of water,52.2° of contact angle of diiodomethane,and 33.1 mJ/m2 of surface free energy with 29.3 mJ/m2 of dispersive components (γL) and 3.8 mJ/m2 of polar components (γsp),respectively. It is found that the electropolymer sized carbon fiber tends to reduce the surface energy due to the decrease of dispersive γL with the increase of the polymer film on the surface of the carbon fiber that plays an important role in improving the mechanical properties of carbon/phenolic resin composites. Compared with the phenolic resin composites reinforced by the unsized carbon fiber,the impact,flexural and interlaminar shear strength of the phenolic resin composites were improved by 44 %,68% and 87% when reinforced with the carbon fiber sized by the electropolymer of m-phenylenediamine,66%,100%,and 112% by the electropolymer of phenol,and 20%,80 %,100% by the electropolymer of acrylic acid. The results indicate the skills of electropolymerization may provide a feasible method for the sizing of carbon fiber in a composite system,so as to improve the interfacial performance between the reinforce materials and the matrix and to increase the mechanical properties of the composites.