With toluene 2, 4-diisocyanate (TDI), polyethylene glycol (PEG) and 2,3-Epoxy-1-prop -anol (glycidol) used as the raw materials, two epoxy terminated polyurethanes (EPU) was synthesized by prepolymerization and closed end. Moreover, EPU with high toughhess is chosen as a coating agent for carbon fiber with three ethylene tetramine (TETA) as curing agen. The influence of the content of crosslinking agent in the coating layer on properties of composites and the mechanism of interface toughness are investigated. The chemical structure and thermal property of the EPU were studied with FTIR, 1HNMR and TGA, respectively. It proves that the thermal stability of EPU is more stable than epoxy coating. The interlaminar shear strength (ILSS) of the sized high modulus carbon fiber/epoxy composites is improved to 71MPa, which increased by 19.4% compared with the composites reinforced by unsized high modulus carbon fiber, and DMTA show that using EPU as a new kind of polymer coating for carbon fiber is a feasible method to improve the interfacial performance of high modulus carbon fiber/epoxy composites.