New-generation Pt/C-TiO₂ nanocomposite electrocatalysts for fuel cells, prepared by a heterogeneous photocatalytic method, have been characterized using techniques such as cyclic voltammetry, rotating disk electrode (RDE) voltammetry, and electrochemical impedance spectroscopy (EIS). Importantly, galvanostatic data confirm the superior stability of these materials against corrosion under anodic polarization conditions relative to commercial benchmark fuel cell electrocatalysts. EIS spectra from ETEK 5, SIDCAT 405 and SIDCAT 410 membrane electrode assemblies (MEAs) were fit to a Randles equivalent circuit with a Warburg element to show the presence of O₂ transport limitation arising from the use of thicker electrodes (lower Pt loading on carbon). The use of a constant phase element (CPE) instead of pure capacitor was justified from the fit procedure as CPE represents the porous electrode system more precisely with its distributive elements. EIS spectra from Tanaka, SIDCAT 451 and SIDCAT 452 MEAs (thinner electrodes) were fit to a Randles circuit with a pure capacitor and no Warburg element. The use of a transmission line model for fitting these data independently provided information about the catalyst layer resistance while all other parameters matched well with that of the Randles circuit. The effective proton transport in cathodes was quantified using polarization data for both classes of MEAs. Trends in the previously reported performance of MEAs prepared using these electrocatalysts were justified based on the relative contributions of kinetic, Ohmic and mass transfer losses to the overall overpotential, which in turn were estimated from impedance and polarization data analyses.