Polyelectrolyte complexes (PECs) of Nafion-H+, a perfluorosulfonic acid ionomer, and Poly(oxyethylene)bisamine (Polyox) were synthesized, and the effect of electrostatic interactions on the physicochemical properties of the individual components was studied using a combination of spectroscopic and electrochemical techniques. More specifically, the pristine PECs were extensively characterized using viscosity, surface tension, and pH measurements and diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy and their transport properties were investigated using cyclic voltammetry and electrochemical impedance spectroscopy, by employing [Fe(CN)(6)](3-) as a redox probe. Acid-base interaction between Nafion and Polyox is evident from pH measurements of the blend solutions, which indicate salt formation at a 50:50 composition, supported further by the existence of a maximum in the plot of surface tension versus blend composition. DRIFT spectra of the PEC membranes indicate subtle changes in the ionic environment and a transition from a state of medium hydration to a partially dehydrated state of the parent ionomer, Nation, after complexation with Polyox. Further evidence for polyelectrolyte-polyelectrolyte association is obtained from cyclic voltammetry, which shows that the interaction between the redox active chromophore, [Fe(CN)(6)](3-), and the pendent sulfonate groups of Nafion is minimized by complexation with the oppositely charged polyelectrolyte Polyox. The water-soluble nature of these PECs along with the tunable range of properties with blend composition could qualify them as suitable candidates for developing stimuli-responsive polymer systems for pharmaceutical and environmental applications.