The constitutive response of perfluorinated sulfonic acid (PFSA) membranes based on tensile testing is investigated, and a phenomenological constitutive model for the elastoplastic flow behavior as a function of temperature and humidity is proposed. To this end, the G’Sell–Jonas (1979, “Determination of the Plastic Behavior of Solid Polymers at Constant True Strain Rate
,” J. Mater. Sci., 14, pp. 583–591) constitutive model for semicrystalline polymers is extended by incorporating, in addition to temperature, relationships between the material constants of this model and the measured relative humidity. By matching the proposed constitutive model to the experimental stress-strain data, useful material constants are found. Furthermore, correlations between these material constants and Young’s modulus and proportional limit stress are investigated. The influence of material orientation, inherited from processing conditions, on the stress-strain behavior is also studied. The proposed model can be used to approximate the mechanical behavior of PFSA membranes in numerical simulations of a fuel cell operation.