In this paper, a microporous-containing graphene oxide/polystyrene (M-GO/PS) was designed and prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of PS from GO surface and then crossrlinking by carbon tetrachloride. The structures of the molecular brush of PS and the related crosslinking M-GO/PS were determined by FTIR, TG, SEM and nitrogen adsorption-desorption analysis. The experimental results showed that PS molecular brush were successfully grown on to the surface of GO. After crosslinking, the PS component was crosslinked into many round nanoparticles with a diameter of 20-30 nm, and therefore the specific surface area of GO/PS obviously increased. This kind of porous M-GO/PS composite was promising for the application in adsorption-desorption energy storage areas.