Development of flexible and freestanding electrode is fascinating for lithium-sulfur (Li-S) batteries to enable higher gravimetric energy density and wider potential applications. However, the lithium polysulfides shuttle effect remains challenging and leads to a severe capacity fading. Here, we study the sulfur cathode prepared via phase inversion method with polyethersulfone (PES) polymeric binder and the coupling strategy of the electrode with polysulfide-modified electrolyte to enhance the cells performance. The flexible/freestanding electrode was successfully prepared by the efficient and straight forward method, even it is possible for massive production of electrodes with various size. The resultant polymeric networks in the electrode can effectively trap the soluble polysulfides owing to the higher hydrophilicity and stronger affinity of PES than that with the routine polyvinylidene fluoride (PVDF) binder. Furthermore, we show a two-fold enhancement of the cell performance by coupling the electrode with polysulfide-modified electrolyte, giving an improved capacity of 1141 mAh g-1, lower polarization of 192 mV and more stable capacity retention with 100% Coulombic efficiency over 100 cycles at 0.25C. The advantages of favored strategy are further demonstrated in lithium-ion sulfur full battery with lithiated graphite anode, which demonstrates much improved performance than those previously reported. This work successfully introduces an efficient strategy for flexible/freestanding electrodes and enlightens the importance of coupling strategy to enhance the performances of Li-S batteries. Figure 1. (a) Digital photographs of the as-prepared composite via phase inversion method. (b) Cycle performance of half-cells using 2-layer PES-CNT-S and PVDF-CNT-S cathodes with polysulfide(PS)-free electrolyte and polysulfide(PS)-modified electrolyte at 0.25C. REFERENCES W. Wahyudi, Z. Cao, P. Kumar, M. Li, Y. Wu, M. N. Hedhili, T. D. Anthopoulos, L. Cavallo, L. J. Li, J. Ming, Adv. Funct. Mater., 2018, 28 (34), 1802244. J. Ming, Z. Cao, W. Wahyudi, M. Li, P. Kumar, Y. Wu, J.-Y. Hwang, M. N. Hedhili, L. Cavallo, Y.-K. Sun, L. J. Li, ACS Energy Lett., 2018, 3 (2), 335-340. W. Wang, Z. Cao, G. A. Elia, Y. Wu, W. Wahyudi, E. Abou-Hamad, A. H. Emwas, L. Cavallo, L. J. Li, J. Ming, ACS Energy Lett., 2018, 3 (12), 2899-2907. Figure 1