The effects of the blend composition and rotation speed on the morphological evolution of polypropylene (PP)/polystyrene (PS) blends were investigated in a twin-screw extruder. When PS was the major component, the rate of melt and the rate of dispersion played final roles in the morphological development of the polymer melts. However, when PP was the major component, the rate of dispersion and the rate of coalescence played key roles. A high tendency to coalesce occurred at a high rotation speed and/or a high content of the dispersed phase. When the PP/PS blend composition was close to 1, a cocontinuous morphology was observed to transmute into a coarse one with increasing rotation speed. Attempts were made to correlate the morphology and mechanical properties.