One kind of side chain liquid crystal epoxy (S-LCE) based on biphenyl mesomorphic unit is synthesized from 2,2-bis(hydroxymethyl)propionic acid,4-phenylphenol,and epichlorohydrin.And the intrinsic thermal conductive liquid crystal epoxy film (LCEF) simultaneously combining with intrinsic self-healing performance is then prepared via thiol-epoxide nucleophilic ring-opening reaction and coating method.1 H NMR and FTIR show that S-LCE and LCEF have been successfully prepared.S-LCE presents nematic liquid crystal from room temperature to 160 ℃.LCEF maintains nematic liquid crystal performance and shows highly intrinsic thermal conductivity & excellent self-healing performance.Thermal conductivity coefficient (λ) values in vertical direction (λ⊥) and parallel direction (λ‖) of LCEF are 0.33 and 1.25 W/mK,respectively,much higher than that of general bisphenol A epoxy resin (E-51,λ⊥ of 0.19 W/mK and λ‖ of 0.65 W/mK).Tensile strength of LCEF is 10.6 MPa,which can maintain at 90.6 ％ and 61.3 ％ after one and four cycles of self-healing behavior,respectively.in addition,LCEF presents a wide service temperature range (-9.8-251 ℃) and good thermal stability (THRI of 148.5 ℃).Simultaneously,LCEF has good transparency,flexibility,and tailorability,expected to be utilized in the fields of flexible electronic devices and intelligent structures.