Through-thickness distribution of liquid crystalline polymer (LCP) of blends containing polyphenylene sulfide (PPS) and LCP was investigated using differential scanning calorimetry and scanning electron microscopy. The effect of the LCP distribution on the mechanical test was checked through bending testing of the various compositions of the injection molded samples. These studies showed a nonuniform distribution of LCP in the PPS-rich region where the LCP content in the skin layer was higher than in the core layer or boundary between the two layers. The LCP component was uniformly distributed in the LCP-rich region. The increase of bending modulus with increasing LCP content was attributed to the reinforcing nature of the LCP fibrils in the skin layer.