Natural rubber (NR)/multi-walled carbon nanotube (MWCNTs) composites were prepared bycombining 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 electrostaticadhesion. In the second assembling, NR/MWCNTs composites were developed by mixing MWCNTs/PDDAsolution with NR latex. The results show that MWCNTs are homogenously distributed throughout the NRmatrix as single tube and present a great interfacial adhesion with NR phase when MWCNTs contents areless than 3 wt%. Moreover, the addition of the MWCNTs brings about the remarkable enhancement in tensilestrength 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 strengthand crosslink both decrease to a certain extent.