The heterocoagulation of latex is a simple and useful method to fabricate various polymer nanocomposites in which a precise control of the colloid stability is essential. In this work, a multi-layered graphenes (MLGs)/poly(styrene-co- butyl acrylate) (P(S-co-BA)) nanocomposite having an excellent dispersion of MLGs was prepared via the sudden heat-ing heterocoagulation process. The P(S-co-BA) component was obtained by emulsion polymerization. This process can effectively shorten the process and particles growth steps. The colloid stability of these dispersions was controlled by factors such as ionic charge, temperature, and reaction times. The influence of these factors on heterocoagulation was evaluated and the properties of the nanocomposites were investigated. The conductivity of the MLGs/P(S-co-BA) nanocomposites increased from -11.53 to -5.70 S/cm for an increase in MLG content from 0.01 to 5 wt%. Moreover, percolation threshold was observed in the case of 0.01 wt% MLGs.