Zein protein is a major coproduct of biofuel from corn. To reduce the brittleness of zein films, a new type of zein-based biomaterial, was synthesized by chemical modification of zein with lauryl chloride through an acylation reaction. The final products were confirmed by (1)H NMR, FT-IR analysis, and SDS-PAGE. Thermal analysis detected no microphase separation in the synthesized polymer matrix. As the content of lauryl moiety increased, the glass transition temperatures of modified zein decreased by as large as 25.8 °C due to the plasticization effect of the lauryl moiety. In addition, mechanical and surface properties of cast films from acylated zein were also investigated. The elongation at break of modified zein sheet was increased by about 7-fold at the high modification level with some loss of mechanical strength. The surfaces of modified zein films were as uniform as unmodified zein film but more hydrophobic, further suggesting that no microphase separation happened during the film formation process. This work indicated the potential of these new biomaterials in the development of biodegradable food packaging materials and delivery systems.