Abstract: Liquid crystal epoxy resin presents high intrinsic thermal conductivity coefficient (λ). However, the complex molecular structure design and tedious synthesis process severely limit its rapid development and further industrial application. In this work, a kind of liquid crystal epoxy (LCE) based on biphenyl mesomorphic unit is synthesized from 4,4’-biphenol, triethylene glycol, and epichlorohydrin. Curing agent of 4,4’-diaminodiphenyl methane (DDM) and boron nitride (BN) fillers are both performed to prepare the intrinsic highly thermally conductive liquid crystal epoxy resin (LCER) and BN/LCER thermally conductive composites via casting method. LCE has been successfully synthesized with expected structure, presenting nematic liquid crystal with range of 135-165oC. LCER shows liquid crystal property with intrinsic λ up to 0.51 W/mK, about 3 times higher than that of general bisphenol A epoxy resin (E-51, 0.19 W/mK). Simultaneously, LCER has good thermal stability with heat resistance index (THRI) being 183.9oC. In addition, the λ values of the BN/LCER thermally conductive composites increase with the increasing loading of BN fillers. When the content of BN fillers is 30 wt%, the λ value of BN/LCER thermally conductive composites is 1.02 W/mK, twice as much as that of pure LCER, also much higher than that of 30 wt% BN/E-51 composites (0.52 W/mK).