The functional characteristics of starch films are significantly influenced by the amylose content and the distribution of the amylopectin chain length. This work used 1,4-α-glucan branching enzyme to molecularly reconstruct corn, pea, and cassava starch in order to examine the association. Films made of both natural and enzyme-modified starch were produced using the casting method. The study investigated the variations in starch films properties and explored the relationship between starch molecular structure and film qualities by correlation analysis. The results showed a significant positive connection (r = 0.954) between the tensile strength and amylose content, as well as a positive correlation (r = 0.939) between the A chains and the elongation at break. The average chain length (r = 0.932) and amylose content (r = 0.902) showed a positive correlation with the degradation temperature, whereas the amylose content (r = −0.946) showed an adverse correlation with the transparency. The B3 chain (r = 0.851) and the average chain length (r = 0.839) both exhibited a positive connection with its contact angle. As a result, our study thoroughly assesses how starch structure affects the characteristics of starch films and offers a fundamental modification pathway for the development of new application areas.