Porous carbon spheres (PCSs) were fabricated through a fast microwave-assisted approach using sucrose as the precursor in a microwave system and subsequent thermal treatment at 600, 800 and 1000 °C. The morphology, structure and electrochemical performance of the PCSs were characterized by scanning electron microscopy, Raman spectroscopy, nitrogen adsorption-desorption, cyclic voltammetry and electrochemical impedance spectroscopy. Their electrosorption performance in NaCl solution was studied and compared with activated carbon, carbon nanotubes, reduced graphene and carbon aerogels. The results show that due to their high specific surface area and low charge transfer resistance, PCSs treated at 1000 °C exhibit high electrosorption capacity of 5.81 m g g−1 when the initial solution concentration is 500 mg l−1, which is higher than those of other carbon materials.