The structure and local organization of new proton conducting ionic liquids (PCILs) obtained by reacting alkylamine with various acids were deciphered by complementary 1- and 2-D heteronuclear NMR experiments. One the one hand, PFG NMR yielded the self-diffusion coefficients of the PCIL components (and thus information on their possible concerted translational motions), while on the other hand, C-13, H-1, and N-15, H-1 correlation and intermolecular Overhauser experiments gave insight into the nature of protonic species and ion-pairing behavior.