Natural rubber (NR)/multi-walled carbon nanotube (MWCNTs) composites were prepared by combining self-assembly and latex compounding techniques.The acid-treated MWCNTs (H2SO4:HNO3=3:1,volume ratio) were self-assembled with poly (diallyldimethylammonium chloride) (PDDA) through electrostatic adhesion.In the second assembling,NR/MWCNTs composites were developed by mixing MWCNTs/PDDA solution with NR latex.The results show that MWCNTs are homogenously distributed throughout the NR matrix as single tube and present a great interfacial adhesion with NR phase when MWCNTs contents are less than 3 wt%.Moreover,the addition of the MWCNTs brings about the remarkable enhancement in tensile strength and crosslink density compared with the NR host,and the data peak at 2 wt% MWCNTs loadings.When more MWCNTs are loaded,aggregations of MWCNTs are gradually generated,and the tensile strength and crosslink both decrease to a certain extent.