Two different supermolecular structures of β-iPP cast films were used to investigate structural evolution during the simultaneous biaxial stretching process via small-angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) spectroscopy. Based on the mechanical behaviors and porosity variations during the stretching process, it was found that the two samples had different structural evolution modes. During the initial stage of deformation, β-hedrites exhibited violent cavitation behavior in the center region of the hedrites by forming elliptical crazes and expanding, while β-spherulites were more inclined to fragment into blocky crystal structures, which was accompanied by the slippage of these structures. In the later stages of stretching, β-hedrites formed numerous dense regions around the elliptical crazes, which hindered microvoid formation and led to a poor pore size distribution. Conversely, β-spherulites generated abundant microfibrillar structures, and abundant microvoids were formed by directly separating the microfibrils, forming a membrane with a superior pore size distribution. The structural evolution of β-iPP with two different supermolecular structures during the simultaneous biaxial stretching process was studied. The two samples showed different structural evolution modes. β-hedrites exhibited violent cavitation behavior during the initial stage of deformation, but in the late stages of stretching β-hedrites formed numerous dense regions, which hindered microvoid formation and led to a poor pore size distribution. Conversely, β-spherulite generated abundant microfibrillar structures, and abundant microvoids were formed, forming a membrane with a superior pore size distribution.