The thermotropic liquid crystalline copolyamide (TLCPa) was synthesized and the in situ composites for TLCPa/Polyamides 66 (PA66) were prepared by melting extrusion. As revealed by differential scanning calorimeter (DSC), depression of the melting point and the crystallinity of PA66 indicated that the miscibility was enhanced via intermolecular H-bonds. Characteristic absorption shifts of C=O groups of TLCPa/PA66 in Fourier transform infra-red spectra (FTIR) confirmed the existence of H-bonds. Scanning electron microscope (SEM) observation showed that the shape of TLCPa phase change in matrix with increasing TLCPa content. Mechanical properties of blends were significantly improved by good interface adhesion and TLCPa fibrils generation.