A novel percolation phenomenon with inorganic nanoparticle loading in polyamide 6-carbon based nanoparticle hybrids was identified. Percolation threshold substantially shifts to lower carbon black (CB) volume fractions in the presence of optimum concentration of chemically modified montmorillonite (organoclay) while the effective organoclay concentration can be optimized to lower the slope of percolation curve maintaining electrical conductivity within static dissipative 10−6–10−9 S cm−1 range. Organoclay/CB ‘nano-unit’ morphology was found in polyamide 6 ternary hybrids. It is composed of stacked organo-montmorillonite platelets that deform to wrap partially around one or two primary CB aggregates. This elementary nano-unit structure induces CB network self-assembly within polyamide 6 matrices. The structure was found to be prevalent throughout the polymer matrix. This morphology remains robust under wide range of thermal-deformation histories due to the strong preferred organoclay/polyamide 6/CB interactions that partially blocks the electron conduction and hopping mechanisms with clay ‘walls’ thereby reducing the slope of the percolation curve. Organoclay can be used as a dispersion control agent in these polymer–carbon systems to induce self-assembly of CB network at low CB content, simultaneously, partial blocking the electron hopping pathways to level the slope of percolation curves. High order exfoliation and nano-scale dispersion of organoclay is essential to induce this advanced percolation phenomenon.