The inclusion of bioactive substances improved the characteristics of chitosan film or adds new functions to it. Chitosan dissolution is a dilemmatic problem because of the low pH of edible solvents and moderate pH of inedible solvents. Procyanidins, a-amylase and starch were added in the film to enhance the antioxidant ability. Sodium bicarbonate was also employed to adjust the pH of acetic acid solution (solvent). Constituent optimisation of the film-forming solution including the pH of solutions with different amounts of sodium bicarbonate, activity of a-amylase at different pH and addition of appropriate amounts of the three main ingredients was performed. The results showed that the solvent pH should be more than 4. The released amount of reducing sugar (starch hydrolyzate) increased with the increase in the amount of enzyme addition. a-Amylase exhibited a more significant effect than procyanidins, increasing the amount of procyanidins. Full-wavelength scanning, optical test, scanning electron microscopy, X-ray diffraction (XRD), infrared (IR) and differential scanning calorimetry (DSC) were performed to measure the film's characteristics. Even the absorbance peak of procyanidins at 280 nm was increased, following its increasing addition amount; the optical values showed no significant difference. Chitosan film containing starch, a-amylase and procyanidins (CSAPW) had a smoother surface than others. Moreover, the micropores observed on CSAPW can be induced by starch hydrolysis in water immersion. The results of X-ray diffraction (XRD), IR and DSC suggested that water immersion provided the environment for enzymes to hydrolyse the starch. In addition, the hydrolysis function induced the destruction of CSAPW's crystal structure, the change of vibration of hydrogen between chitosan, starch, procyanidins, water and the variation of water evaporation temperature.