TDI as main isocyanate, IPDI as end-capping reagent, waterborne polyurethane (WPU) surface-sizing agent have been obtained by a pre–polymerization process. WPU were mixed with starch SSA in different proportion and a composite sizing agent obtained. It is indicated the water resistance, gloss and folding resistance of WPU/starch sized papers are much higher than starch sized papers. The ink absorption obviously decreases and the mechanical properties wholly increase. WPU/starch composite emulsions is a new kind of surface sizing agent having broad development prospects.