A ternary composite of poly(lactic acid) (PLA), poly(caprolactone) (PCL), and carbon black (CB) shows the PCL-induced CB self-aggregation and percolation formation when the amount of the PCL phase as the secondary phase is as small as the amount of CB. Furthermore, when the drop size of the PCL phase becomes smaller, the ternary composite forms a percolation of high order structure, resulting in a remarkable enhancement of the electrical conductivity (~4 × 10−2 S/m with 4 wt.% CB). To further control the percolation structure, the composite fabrication is controlled by splitting a typical single-step mixing process into two steps, focusing on the dispersion of the secondary PCL phase and the CB particles separately. Under the single-step mixing protocol, the ternary composite shows a structure with greater CB aggregation in the form of a high aspect ratio and large aggregates (aggregate perimeter~aggregate size 0.7). Meanwhile, the two-step mixing process causes the CB aggregates to expand and create a higher structure (aggregate perimeter~aggregate size 0.8). The reduced size of the secondary phase under a mixing condition with high shear force prior to the addition of CB provides a larger interfacial area for CB to diffuse into the PCL phase during the subsequent mixing step, resulting in a further expansion of CB aggregation throughout the composite. The particle percolation of such a high order structure is attributed to high storage modulus (G′), high Young’s modulus, high dielectric loss (ε″), and negative–positive switching of dielectric constant at high frequency (of 103 Hz) of composite.