We investigated the thermophysical and electrochemical properties of eight model protic ionic liquids (PILs) primarily because of our interest in their proton conductivity and low volatility. The chemical structures of the cations (ammonium vs imidazolium) and anions (mesylate vs triflate) were found to strongly govern properties such as density, viscosity, ionic conductivity, thermal and electrochemical stability, and phase transition behaviors. Structure-property relations were analyzed on the basis of charge delocalization, cation pi-stacking, van der Waals interactions of alkyl tails, and hydrogen bonding interactions between cations and anions. The diffusion coefficients of the free proton, the cation, and the anion were determined by using NMR spectroscopy, and were used to differentiate between the vehicular and Grotthuss mechanisms of diffusion of protons. A correlation, based on the Sutherland-Einstein equation, Was developed to predict ionic conductivity by using the room temperature molar volume and the VFT equation for viscosity.