Compared with conventional surface sizing agents, polymers surface size agents are good film and printing quality. In this work, different types of SMA (Styrene Maleic Anhydride) from the United States Hercules and Sartomer companies were investigated. Firstly, each of SMA sizing agents was studied respectively for choosing the optimized SMA depending on the improvement of physical and ink-jet printing properties, and then the effects of different formulation surface size agents containing the optimum SMA and cationic starch on paper and ink-jet printing properties were also studied in order to analyzing the synergism effects of the two surface size agents. The results show that S520 was better than several other SMA surface sizing agents in the improvement of physical properties and ink-jet printing performance of paper. S520 could produce good film property which could reduce the paper permeability, improve smoothness have less loss whiteness and opacity. It could also enhance the color density, expand the scope of the dark tone and improve dots clarity degree of printed paper.