The award-winning hydrocarbon-based PEM, Pemion®, produced by Ionomr Innovations, is nested at the center of these exciting developments. Mechanically reinforced composite membranes are produced at scale utilizing advanced roll-to-roll manufacturing techniques, affording a hydrocarbon-based PEM that, for the first time, exhibits performance parallel to or greater than incumbent perfluorinated sulfonic acid (PFSA)-based PEMs. These developments, however, would not be possible without powerful characterization methods such as electrochemical impedance spectroscopy (EIS). Assessments of a membrane’s in-plane and through-plane proton conductivity are used to derive valuable insight to its constituents, the ion-conducting ionomer and chemically-inert mechanical reinforcement, as well as their interrelation. The anisotropic nature of the composite membranes is probed via comparison of in-plane and through-plane conductivity. The sensitivity of through-plane conductivity measurements to experimental parameters such as cell pressure are probed, and a new cell design is realized to reduce measurement error. These data help identify favorable and unfavorable material processing and manufacturing techniques, and their implications to in-situ fuel cell performance. The net consequence of these findings is establishing EIS as a core component of an iterative material design and production process for output of consistent, high-performance PEMs.