High-quality and free-standing polyimide (PI) film with desirable mechanical properties and uniformity is in high demand due to its widespread applications in highly precise flexible and chip-integrated sensors. In this study, a free-standing PI film with high toughness was successfully prepared using a diamine monomer with ether linkages. The prepared PI films exhibited significantly superior mechanical properties compared to PI films of the same molecular structure, which can be attributed to the systematic exploration of the film-forming process. The exploration of the film-forming process includes the curing procedures, film-forming substrates, and annealing treatments. Additionally, the thickness uniformity and surface homogeneity of free-standing films were crucial for toughness. Increasing the crystallinity of the PI films by eliminating residual stress also contributed to their high strength. The results demonstrate that by adjusting the above-mentioned factors, the prepared PI films possess excellent mechanical properties, with tensile strength and elongation at break of 194.71 MPa and 130.13%, respectively.