Hollow fiber membranes were prepared via thermally-induced phase separation process followed by stretching process from isotactic polypropylene and soybean oil system. Various operating parameters were examined in terms of their effects on the structure variation and performances of the membrane, and were optimized, Melt viscosity of the melt sample had influence on the formation of the microfibrils, and addition of nucleating agent increased the nucleation density to enhance the interspherulitic pore formation by stretching. Annealing the membrane at its stretched state relaxed the stress induced by stretching and helped the membrane maintain the stretched structure without shrinking. Solid-liquid phase separation is more prevalent when the nucleating agent was added, and coagulation bath temperature determined the nucleation density, which affected the pore formation by stretching. In the absence of nucleating agent, nucleation was net effective and liquid-liquid phase separation governed the structure formation which showed the opposite trend to that of the case with nucleating agent.