In this article, copper (Cu) crystallites were successfully prepared via low temperature molten salt method, and the possible formation mechanisms were proposed. The conductive fillers of multiwalled carbon nanotubes (MWCNTs) and as‐prepared Cu particles were designed and introduced into acrylonitrile‐butadiene‐styrene (ABS) blend to prepare different conductive composites. The dispersion states of conductive fillers and the morphologies of the composites were characterized using a field emission scanning electron microscope. The electrical resistivity of different composites was measured. The results showed that Cu and MWCNTs exhibited a synergistic effect in decreasing the electrical resistivity of the Cu/MWCNTs/ABS composites, because Cu that could locate between MWCNTs chain segments provides a better charge transport in the conductive pathways. Compared with pure ABS, the tensile strength, elastic modulus and thermal stability of the Cu/MWCNTs/ABS composites were significantly improved with the incorporation of Cu and MWCNTs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41738.