The last decade has witnessed significant breakthroughs in the synthesis of porous carbon spheres (PCSs). This Review provides an updated summarization on the controlled synthesis of PCSs for supercapacitors. The synthetic methodologies can be generally categorized into (i) hard templating, (ii) soft templating, (iii) the modified Stöber method, (iv) hydrothermal carbonization (HTC), and (v) aerosol-assisted methods. The obtained PCSs include microporous/mesoporous/macroporous carbon spheres, single-/multi-shelled hollow carbon spheres, and yolk@shell carbon spheres. The structure-electrochemical performance correlation is discussed. Finally, the future research directions on the rational design of PCSs for supercapacitors are predicted.