Unraveling the fundamentals of Li-O(2) battery chemistry is crucial to develop practical cells with energy densities that could approach their high theoretical values. We report here a straightforward chemical approach that probes the outcome of the superoxide O(2)(-), thought to initiate the electrochemical processes in the cell. We show that this serves as a good measure of electrolyte and binder stability. Superoxide readily dehydrofluorinates polyvinylidene to give byproducts that react with catalysts to produce LiOH. The Li(2)O(2) product morphology is a function of these factors and can affect Li-O(2) cell performance. This methodology is widely applicable as a probe of other potential cell components.