Polymer-dispersed liquid crystal(PDLC)films comprising polyvinyl alcohol(PVA)and liquid crystal monomer(LCM)were successfully obtained by the method of solution casting&thermal compress-ing.LCM was distributed orderly in PVA matrix by hydrogen bond interaction,to form PVA-LCM interpenetrating-layered networks.When the mass fraction of LCM was up to 35 wt％,the corresponding in-plane thermal conductivity coefficient(λ∥)of PDLC film was significantly increased to 1.41 W m-1 K-1,about 10.8 times that of neat PVA(0.13 W m-1 K-1).High intrinsic λ//values of PDLC films were mainly attributed to the formed microscopic-ordered structures from ordered stacking of LCM,ordered arrangement of PVA chains,and their hydrogen bond interaction.This work would offer a new way to design and prepare novel intrinsic high thermal conductive polymers.