Carboxymethyl starch with lower degree of substitution was, blended with acrylate copolymer for revealing the relation between mechanical properties and chemical structure of blending film. Effects of carboxymethylation of starch, acrylate constituent units of acrylate copolymers, and copolymer content of the film on the properties were investigated. The mechanical properties were evaluated in terms of tensile strength, breaking elongation, abrasion resistance, and flex-fatigue resistance. Film morphology was examined with X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscope (AFM). It was found that the properties depended on the degree of substitution of carboxymethyl starch, chemical structure of acrylate units, and content of acrylate copolymer. Phase-separation of the two ingredients occurred within film matrix and the separation was decreased after starch carboxymethylation. Breaking elongation and flex-fatigue resistance of the film reached maximums when acrylate copolymer content was 50%. Excessively increasing the content of acrylate copolymer reduced the film properties.