The synthesis of metal-free heterogeneous catalyst in environmental catalysis has become a hot area of research. To achieve the goal of sustainable recycling of biological resources and mitigation of greenhouse gases, a novel metal-free cellulose based Schiff-base heterogeneous catalyst (Cell-L-2) is reported in the ring-opening addition reaction of CO2 with epoxides to synthesize cyclic carbonates for the first time. The as-prepared samples were characterized by Fourier-transform infrared, X-ray photoelectron spectroscopy, scanning electron microscope, Brunauer-Emmett-Teller/Barrett-Joyner-Halenda, solid-state NMR, and thermogravimetric analysis analyses. The successful anchoring of nonmetal Schiff-base complex on chlorinated cellulose is evident from the structural composition studies. The catalytic activity results showed that the samples exhibited excellent catalytic performance in the solvent-free condition. The yield of resultant propylene carbonate was measured to be 98.7% with similar to 100% selectivity. The enhanced role of the present catalyst for the ring-opening addition could be attributed to the synergy of its structural hydroxyl, phenolic -OH, and Lewis basic (imine) groups in the catalyst, which are capable of activating the epoxide and CO2, which efficiently participate in the reaction together with the substantial role of nucleophilic ionic (Br-) group from the co-catalyst. The catalyst was effectively reused for five consequent runs without a significant loss in the catalytic activity and showed high effectiveness for a series of other epoxides.