This study investigates the effects of modifying commercial Nafion-212 thin films with dodecyltriethylammonium cation (DTA+) on their electrical resistance, elastic modulus, light transmission/reflection and photoluminescence properties. The films were modified through a proton/cation exchange process for immersion periods ranging from 1 to 40 h. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were employed to analyze the crystal structure and surface composition of the modified films. The electrical resistance and the different resistive contributions were determined via impedance spectroscopy. Changes in the elastic modulus were evaluated using stress–strain curves. Additionally, optical characterization tests, including light/reflection (250–2000 nm) and photoluminescence spectra, were also performed on both unmodified and DTA+-modified Nafion films. The results reveal significant changes in the electrical, mechanical and optical properties of the films, depending on the exchange process time. In particular, the inclusion of the DTA+into the Nafion structure improved the elastic behavior of the films by significantly decreasing the Young modulus. Furthermore, the photoluminescence of the Nafion films was also enhanced. These findings can be used to optimize the exchange process time to achieve specific desired properties.