We report on the physical properties of films synthesized with native corn starch (NCS) and resistant starch (RS4) prepared with NCS. NCS and RS4/poly(-vinyl alcohol) (PVA) blend films were synthesized with a mixing process and casting method. Glycerol (GL) and citric acid (CA) were used as additives. Glutaraldehyde (GLU) was used as a crosslinking agent of the films. RS4 was synthesized with sodium trimetaphosphate and sodium tripolyphosphate as a crosslinker. Then, the RS4 thus synthesized was confirmed by the pancreatin-gravimetry method, swelling power, differential scanning calorimetry, and X-ray diffraction. The tensile strength, elongation, swelling behavior, and solubility of the films were measured. The results of the measurements indicated that the RS4-added film was better than the NCS-added film. In particular, the RS4/PVA blend film with CA as an additive showed physical properties superior to those of the other films. Also, the physical properties with GLU added as a crosslinking agent to the films were investigated. With increasing GLU contents, the tensile strength increased but the elongation, swelling behavior, and solubility values of the GL-added and CA-added films decreased.