The effect of high-temperature spinning and poly(vinyl pyrrolidone) (PVP) additive on poly(vinylidene fluoride) (PVDF) hollow fiber membranes was investigated using differential scanning calorimetry, X-ray diffraction measurement, and scanning electron microscopy, together with the corresponding microfiltration performances such as water flux, rejection rate, and elongational strength. Using high-temperature spinning, porous hollow fiber membranes with particulate morphology were prepared through PVDF crystallization. The particulate structure of the membranes was further modified by the addition of miscible PVP with PVDF. Due to these effects, the rejection rate and strength of the fibers were increased at the expense of reduced water flux and mean pore size, which indicates that high-temperature spinning and PVP addition are very effective to control the morphology of PVDF hollow fiber membranes for microfiltration.