Poly (phenylene sulfide) (PPS)/nano-TiO2 composites were prepared by DAKA miniature blending instrument. Isothermal crystallization behavior of PPS composites at 245°C, 250°C, 255°C and 260°C were investigated by means of DSC. The crystallization time of PPS composites is shorter than which of neat PPS at the same crystallization temperature. The Avrami equation was used to analyze DSC data. Results showed that neat PPS is homogeneous nucleation at lower crystallization temperature, which is heterogeneous nucleation at higher crystallization temperature contrarily. PPS/nano-TiO2 composites are heterogeneous nucleation at various crystallization temperature, nano-TiO2 particles play a role of nucleating agent.