Abstract: This paper reviewed the latest research progress in heat-conductive crosslinking-polymers and analyzed the phonon heat transfer mechanism and influencing factors on heat conduction of intrinsic polymers. Furthermore, the paper mainly discussed the methodology for enhancing the thermal conductivity of cross-linked polymers, which included the introduction of the prepolymer and curing agent with ordered structure units, the incorporation of liquid crystal or mesogenic units into the cured networks to form local microscopically-ordered structures, and the construction of heat conductive pathways through nonbonding inter-chain interactions by choosing proper crosslinker for the networks. Finally, the further direction in development of the intrinsic heat-conductive cross-linked polymers was mentioned.