Blends of a new phenolphthalein poly (ether sulfone) (PES-C) and a thermotropic liquid crystalline polymer (LCP) were prepared by melt-blending in a twin-screw extruder. Rheological properties, fracture toughness, K(IC), and morphology of the blends were studied. It was found that the addition of LCP could reduce the melting viscosity and improve the fracture toughness of the PES-C matrix. The morphology of the LCP phase for the fractured section changed with increasing LCP content in the blend from dropletlike to fibrillar and layered structure. Strong interfacial adhesion could be observed at a lower content of LCP. The toughening mechanisms by blending LCP were also discussed.