In previous studies, the photografting polymerization of vinyl acetate (VAC) and maleic anhydride (MAH) was investigated systematically. After that, to increase the grafting rate and efficiency and make the project more practicable, a VAC-MAH binary monomer system was employed for simultaneous photografting onto the surface of low-density polyethylene film. The effects of several crucial factors, including the composition and total concentration of the monomer solution and different types of photoinitiators and solvents, on the grafting polymerization were investigated in detail. The conversion percentage (CP), grafting efficiency (GE), and grafting percentage were measured by gravimetry. The results showed that the monomer composition played a big part in this binary system; appropriately increasing the content of MAH in the monomer feed was suited for grafting polymerization. The growth of the total monomer concentration, however, made the copolymerization faster and was unfavorable for grafting polymerization. The three photoinitiators-2,2-dimethoxy-2-phenylacetophenone (Irgacure 651), benzoyl peroxide, and benzophenone (BP)-led to only slight differences in CP, but for GE, BP was the most suitable. As for the different solvents-acetone, ethyl acetate, tetrahydrofuran (THF), and chloroform-using those able to donate electrons (acetone and THF) resulted in relatively higher CPs; on the contrary, the use of the other solvents made GE obviously higher, and this should be attributed to the charge-transfer complex (CTC) that formed in this system. (C) 2004 Wiley Periodicals, Inc.