A small size effect could be conducive to enhancing the electrochemical performance, while the mechanism by which they also increase the capacitance for carbon electrode materials has not been established. Here, ultrasmall polyacrylonitrile particles with controllable sizes are supported on poly(ionic liquid)s microspheres (PILMs/PAN) by epitaxial polymerization growth strategy. Unlike traditional subtraction formulas in developing a porous architecture, we report on the synthesis of creating numerous micro/mesopores in carbon materials by addition theorem, and thus making for the perfection of packing density, which has not been reported yet. As an example, PILMC/PAN-L with a well-balanced specific surface area of 875.38 m² g⁻¹ and packing density of 1.05 g cm⁻³ demonstrated gravimetric and volumetric capacitances of 309 F g⁻¹ and 324.45 F cm⁻³ at 0.5 A g⁻¹, showing good rate performance and stable cyclability. Moreover, the underlying mechanism is thoroughly developed using multiple electrochemical methods. On this basis, this work would afford avenues to further enhancing the electrochemical performance, especially in exploring advanced carbon materials.