Lithium/sulfur batteries in Lithium Metal Polymer (LMP) technology suffer from poor reversibility and important capacity fade. In this paper we studied structural evolutions of Li/S cells with PEO-based (poly(ethylene oxide)) dry polymer electrolyte, by means of scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). Discharge occurs along with dissolution of the active material into soluble polysulfides in PEO. Diffusion of the sulfide species results in important volume changes of both the electrode and the electrolyte. This eventually leads to collapse of the electrode upon a few cycles, which contributes to the poor cyclability of the battery. In order to prevent this phenomenon, the mechanical strength of the cathode was enhanced by adding poly(vinylidene fluoride) (PVDF) in its composition. However, although PVDF helps maintaining the electrode's structure, it could not completely solve the cyclability issue.