The sulfur cathode in traditional lithium–sulfur batteries suffers from poor cyclability due to polysulfide shuttling effect as well as large volume change during charge/discharge processes. Gum arabic (GA), a low cost, nontoxic, and sustainable natural polymer from Acacia senegal, is adopted as a binder for the sulfur cathode to address these issues. The excellent mechanical properties of GA endow the cathode with high binding strength and suitable ductility to buffer volume change, while the functional groups chemically and physically confine sulfur species within the cathode to inhibit the shuttling effect of polysulfides. Additionally, GA shifts the electrode fabrication process from the organic solvent process to an aqueous process, eliminates the use of toxic organic solvents, and achieves uniformly distributed electrode with lower impedance. A remarkable cycling performance, i.e., 841 mAh g−1 at low current rate of C/5, is achieved throughout 500 cycles due to the bifunctions of the GA binder. The gum arabic (GA) binder‐based sulfur cathode (75 wt% sulfur) is evaluated under long‐term cycling at C/5. The excellent mechanical properties of GA endow the S@GA cathode with high binding strength and suitable ductility to buffer volume change, while the functional groups chemically and physically confine sulfur species within the cathode to inhibit the shuttling effect of the polysulfides.