In this work, the stability of ether-based electrolytes for Li-S batteries is investigated with particular regard to the effect of dissolved oxygen. Specifically, the performance of two different electrolyte solvents, i.e., 1,2-dimethoxyethane and its mixture with 1,3-dioxolane (DME: DOL, 1:1 v/v), is characterized in cells assembled in dry air environment, which would substantially lower production costs with respect to inert atmosphere (Ar). Although stability of all the components would suggest that Li-S batteries built in both the environments should behave similarly, it is found that cells containing the DME: DOL-based electrolyte are rather unstable in the presence of O-2 in contrast to those employing DME-based electrolyte, which show a relatively good performance. The different sensitivity toward O-2 of these electrolytes is associated to the ring-opening reaction of DOL, which happens to a greater extent when O-2 is present, but occurs also in its absence. Based on these results a mechanism for electrolyte degradation in Li-S cells, and its reaction with dissolved polysulfides is proposed, which rationally explain for the first time the behavior already reported in literature for these kind of batteries. These findings are also relevant to the field of Li-O-2 batteries, where these ether-based electrolytes are also used. (C) The Author(s) 2017. Published by ECS. All rights reserved.