AbstractBlends of polyphenylene sulfide (PPS) with a commercial, wholly aromatic, liquid crystal copolyesteramide (Vectra‐B950) have been prepared by meltblending. The crystallization behavior of neat and blended PPS has been studied by differential scanning calorimetry (DSC), under both non‐isothermal and isothermal conditions. It has been found that blending PPS with Vectra‐B leads to an increase of the temperature of non‐isothermal crystallization and to a pronounced acceleration of the isothermal crystallization, without any reduction of the degree of crystallinity. All these effects have been found to occur independent of the Vectra‐B concentration, within the investigated range (2 to 20%, w/w). The results have been interpreted in terms of an incrased nucleation density of the blends, probably due to heterogeneous substances, initially present in the Vectra‐B bulk, which dissolve to saturation in the PPS phase, during me