A heat pipe facilitates thermal dissipation for various applications. It is based on the phase change heat transfer and the surface morphology of the inner structures is a dominant factor to determine thermal performances. Recently, micro-nanotextured cotings comprising multi-porous structures have attracted as new interface layers to improve the thermal characteristics of heat pipes. However, the fabrication of these micro-nanotextured surfaces on substrates generally require bulky setup that incurs high-cost and long-processing time. Herein, we report layer-by-layer (LbL) assembled hybrid structures, which are fabricated by solution-processing at room temperature, without high temperature or vacuum processing. The hybrid structures as biporous coatings of multi-wall carbon nanotube (MWCNTs)/ZnO nanoparticles and MWCNTs/PEI-MWCNTs films were deposited on the inner surfaces of circular heat pipe which was covered by micro-sized sintered-copper particles. the effects of ZnO and PEI were discussed by the comparison of thermal performances. Both LbL-assembled coatings improved both heat transfer coefficient and stable operating range