A custom-built apparatus for performing rotating disk electrode voltammetry (RDE) using vapor-deposited, epitaxial, thin film samples as rotating electrodes is described. This method allows for quantitative electrochemical characterization using thin film samples, including those deposited on insulating substrates, and allows for very facile exchange of samples. Cyclic voltammetry and RDE voltammetry of iron ferricyanide in aqueous media were explored to examine if the system causes unusual deviations from ideal hydrodynamic voltammetric behavior. The set-up was also used to examine the ORR activity of a platinum thin film as a model system for a higher-current reaction, relevant to fuel-cell research. Both studies indicated that the set-up did not cause any deviations from anticipated RDE behavior, demonstrating that this is a viable method for performing rotating disk electrode voltammetry of vapor-deposited thin films, with emphasis on those relevant to fuel cell research. The set-up was used to investigate/test the ORR and OER activity of a series of A(2)B(2)O(7) pyrochlore samples. (c) 2017 The Electrochemical Society.