A systematic investigation is reported into the influence of the counter cations on the optical, electrical and electroluminescent properties of polyelectrolytic conjugated polymers and of their cyclodextrin-threaded rotaxanes. We compare conjugated polyelectrolytes with sulfonated side groups where the anionic charge is balanced by Li+, K+, Cs+, tetramethylammonium (Me4N+) and cryptate-encapsulated potassium (K+@[2.2.2]). Narrowing (for the unthreaded analogues) and a slight red-shift of the absorption spectra (for the rotaxanes) are found upon exchange of Li+ for larger cations, together with a blue-shift and an efficiency enhancement of the luminescence. These effects are similar in nature to those induced by rotaxination, and are therefore assigned to a marked reduction of intermolecular interactions between the conjugated cores. Exchange of Li+ for K+, Cs+, or Me4N+ results in a higher electroluminescence external quantum efficiency (EQE) for both polyrotaxanes and unthreaded polymers. For polyrotaxane-based devices the EQE increased approximately 7 times upon substitution of Li+ with Cs+ or Me4N+, thereby demonstrating the importance of the selection of the counter-cations for optimizing the performance of polyelectrolytic conjugated polymers in light-emitting devices.