A lot of investigations calculate that fullerene would be an excellent unit for porous adsorbents for gas sorption and separation. Although the conjugated structure and symmetrical shape of fullerene makes it an ideal building block, there is no facile strategy to achieve fullerene-based porous materials. Herein, we adopt a novel acid catalyzed coupling reaction to bind the fullerene molecules together in a one-step synthesis. After synthesizing the adducts as models, the atomic connectivity between the fullerene molecules is determined clearly. We then prepared a series of fullerene-based porous aromatic frameworks (PAFs). The targeted products adsorb H2 and CO2, and they exhibit some selectivity of CO2 over N2 and CH4. The good performance of the PAFs indicates that we could combine the gas binding ability of the building block and the porous nature of PAF materials together to give a better adsorbent.