Oxygen gain is the difference in fuel cell performance operating on oxygen-depleted and oxygen-rich cathode fuel streams. Oxygen gain experiments provide insight into the degree of oxygen mass-transport resistance within a fuel cell. By taking these measurements under different operating conditions, or over time, one can determine how oxygen mass transport varies with operating modes and/or aging. This paper provides techniques to differentiate between mass-transport resistance within the catalyst layer and within the gas-diffusion medium for a polymer-electrolyte membrane fuel cell. Two extreme cases are treated in which all mass transfer limitations are located only (i) within the catalyst layer or (ii) outside the catalyst layer in the gas diffusion medium. These two limiting cases are treated using a relatively simple model of the cathode potential and common oxygen gain experimental techniques. This analysis demonstrates decisively different oxygen gain behavior for the two limiting cases. For catalyst layer mass transfer resistance alone, oxygen gain values are limited to a finite range of values. However, for gas diffusion layer mass transfer resistance alone, the oxygen gain is not confined to a finite range of values. This analysis is then extended to evaluate ionic effects within the catalyst layer. / text