The objectives of this paper are to understand the crystallization behavior of polypropylene (PP) composites with surface modified tetra-needle-shaped zinc oxide whisker (T-ZnOw). T-ZnOw was surface modified with different coupling agents, such as silane coupling agents (KH-550, KH-560) and titanate coupling agent (NDZ-105), in order to improve the compatibility between PP and T-ZnOw. DSC and POM were used to characterize the melt and crystallization behavior and the crystalline structures of the composites, respectively. The results show that the surface modified T-ZnOw acts as a nucleating agent of PP crystallization, depending on the coupling agent used for modification. KH-550 and KH-560 have more apparent role in improving the interfacial interaction than NDZ-105 and induce PP crystallization at higher temperature and with smaller spherulites size. The results also suggest that the crystallization behavior depends on not only the content of coupling agent, but also the content of the surface modified T-ZnOw used in the composites.