We have provided a design of the macroscopic morphology of carbon nanotubes (CNTs) using emulsion droplet confinement. The evaporation of CNT-dispersed aqueous emulsion droplets in oil produces spherical CNT assemblies, i.e., CNT balls. In this emulsion-assisted method, compact packing of CNT was obtained by the presence of capillary pressure during droplet evaporation. The size of the CNT balls could be controlled by changing the concentration of the CNT dispersion solution; typically, CNT balls with an average size in the range of 8-12 μm were obtained with a Brunauer-Emmett-Teller (BET) specific area of 200 m(2)/g. Heat treatment of the CNT balls, which was required to remove residual solvent, and cement CNTs was followed, and their effect has been characterized; the heat treatment at high temperature desorbed surface oxygenated groups of CNTs and created defective carbon structures, but did not change pore structure. The dispersion of CNT balls was applied to form CNT ball-assembled film for a supercapacitor electrode. The specific capacitance of 80 F/g was obtained at 500 °C heat treatment, but the CNT balls prepared at a higher temperature actually decreased the capacitance, because of the removal of surface oxygenated groups, thereby decreasing the pseudo-capacitance. The capacitive properties of CNT ball-assembled electrodes were compared to CNT films; the CNT ball electrodes showed 40% higher specific electrochemical capacitance and higher rate performance, which is attributed to the compact packing of CNTs in the CNT ball and the hierarchical porous structures in the ball assemblies.