Thermotropic liquid crystalline polyarylate (TLCP) is a high-performance engineering plastics with many excellent properties, but its low thermal conductivity limits its application in thermal management materials. In this study, based on the principle of acetylation-melt ester exchange segmented reaction, the acetylated monomers of p-hydroxybenzoic acid and 6-hydroxy-2-naphthalenecarboxylic acid: p-acetyloxybenzoic acid (ABA) and 6-acetyloxy-2-naphthalenecarboxylic acid (ANA) were prepared firstly, and the thermally liquid crystalline polyarylene ester (TLCP) were prepared from acetylated monomers. A twin-screw extruder is used to build an anisotropic controllable three-dimensional thermal conduction network by utilizing the shear-induced orientation effect during TLCP melt processing, and the controllable blending of hexagonal boron nitride (h-BN) and TLCP is realized. TLCP/h-BN composite. The results show that the thermal conductivity in the in-plane direction of the TLCP/h-BN composites is enhanced to the highest 0.92 W/(m·K) when the addition amount of h-BN is 30 wt%, and the sample also has excellent mechanical properties and thermal stability with a tensile strength of 152.99 MPa and a thermal decomposition temperature (Td5) of 492.33 ℃, which has a wide range of application prospects in thermal management materials.