The fine structures of pumpkin, potato, wheat, cassava, and pea starches were determined, followed by an evaluation of how these structures affected the properties of starch films. The structures significantly influenced film properties. Starches with larger molecular weights exhibited greater thermal stability. The tensile strength of starch film was negatively associated with the amylose chain length (r = -0.88, p < 0.05). The chain length distributions of amylose and amylopectin affected the mechanical properties of starch films by influencing structure ordering, supported by the positive correlation between the double helix content and the tensile strength (r = 0.95, p < 0.05). The amylopectin B1, B2, and B3 chains increased film mechanical strength. Conversely, amylopectin A-chains reduced the mechanical strength. The water contact angle was negatively correlated with the B3 chain proportion (r = -0.93, p < 0.05). The pumpkin starch exhibited the highest tensile strength (14.29 MPa), while the wheat starch film showed the highest water contact angle (112°). This study offers valuable insights into the structure-function relationships of starch films, thereby facilitating the acquisition of starch films with enhanced strength and stability through screening or designing starch structures. Consequently, this will expand the application of starch films as packaging materials in various food products.