The isothermal crystallization kinetics, the morphology, and the melting behavior of melt-processed composites of poly(phenylene sulfide) (PPS) with a thermotropic liquid crystalline copolyester, Vectra A950, (TLCP) were studied by differential scanning calorimetry (DSC) and optical microscopy. The crystallization behavior of PPS in PPS/TLCP composites is observed to be highly sensitive to T-c and immiscible TLCP content in the composites. The spherulite growth rate, the overall crystallization rate, and the activation energy of PPS in PPS/TLCP composites are markedly depressed by the presence of TLCR The analysis of the Avrami kinetic parameters (n and k) indicates that blending of TLCP with PPS causes heterogeneous growth process and nucleation mechanisms. At low T(c)s, the PIPS crystallization rate is faster than that neat PPS with <= 30 wt% TLCP loading whereas at high Tcs it remains almost unchanged. The analysis of the melting behavior of these composites indicates that the stability of PPS crystals and their reorganization is influenced both by the T(c)s and the composite compositions. The sizes and the number of spherulites change a great extent with composite composition with a drop of spherulite rapid growth rate, at constant T-c, with increasing content of TLCP in composites. The analysis based on the Lauritzen-Hoffmann secondary nucleation theory, using present DSC data, indicates that present data predominantly follow a linear growth trend over a present range of T(c)s and PPS crystallization in composites still occurs according to regime II kinetics, whereby multiple surface nuclei form on the substrate with multiple nucleation acts commencing before initially formed growth layer is completed. The fold surface free energy of PPS chains in composites is found higher than that of neat PPS, leading to an average higher work of chain folding and is ascribed to a general development of the PPS chain mobility in the composite melt. POLYM. ENG. SCI., 49:397-417, 2009. (C) 2008 Society of Plastics Engineers