Cross-linked ionomer networks of varying poly (ethylene glycol) diacrylate cross-linker chain length, ionic comonomer chemistry, and comonomer ratio have been studied for their use as polysulfide shuttle inhibiting separators in magnesium-sulfur (Mg-S) batteries. Through the use of X-ray scattering, polysulfide diffusion experiments, conductivity measurements, and Mg-S cell cycling, it was determined that inclusion of tethered anions in polymer networks mitigates the polysulfide shuttle effect. Polysulfide crossover through networks into a bulk electrolyte can be reduced by absorption into the polymer gel, steric rejection, and electrostatic rejection, with the predominance of these mechanisms dictated by polymer composition and structure. The best network composition allowed an initial Mg-S cell discharge capacity of 522 mAh/g compared to a discharge capacity of 365 mAh/g using a literature standard glass fiber separator. The ionomer cell saw 67% capacity retention after three cycles, whereas the glass fiber separator could not complete the first charging cycle due to the polysulfide shuttle.