Sodium-Sulfur (Na-S) batteries are outstanding for their ultrahigh capacity, energy density, and low cost, but they suffer from rapid cell capacity decay and short lifespan because of serious polysulfide shuttle and sluggish redox kinetics. Herein, we synthesize thin films of covalent organic frameworks (COFs) with azobenzene side groups branched to the pore walls. The azobenzene branches deliver dual functions: (1) narrow the pore size to the sub-nanometer scale thus inhibiting the polysulfide shuttle effect and (2) act as ion-hopping sites thus promoting the Na + migration. Consequently, the Na-S battery using the COF thin film as the separator exhibits a high capacity of 1295 mA h g -1 at 0.2 C and an extremely low attenuation rate of 0.036% per cycle over 1000 cycles at 1 C. This work highlights the importance of separator design in upgrading Na-S batteries and demonstrates the possibility of functionalizable framework materials in developing high-performance energy storage systems.