Isotactic polypropylene (iPP) hollow fiber microporous membranes were prepared using thermally induced phase separation (TIPS) method. Di-n-butyl phthalate (DBP), dioctyl phthalate (DOP), and the mixed solvent were used as diluents. The effect of alpha (DOP mass fraction in diluent) on the morphology and performance of the hollow fiber was investigated. With increasing alpha, the morphology of the resulting hollow fiber changes from typical cellular structure to mixed structure, and then to typical particulate structure. As a result, the permeability of the hollow fiber increases sharply, and the mechanical properties of the hollow fiber decrease obviously. It is suggested that the morphology and performances of iPP hollow fiber microporous membrane can be controlled via adjusting the compatibility between iPP and diluent.