For a comparison of the interaction modes of various chalcogen-bond donors, 2-chalcogeno-imidazolium salts have been designed, synthesized, and studied by single crystal X-ray diffraction, solution NMR and DFT as well as for their ability to act as activators in an SN1-type substitution reaction. Their interaction modes in solution were elucidated based on NMR diffusion and chemical shift perturbation experiments, which were supported by DFT-calculations. Our finding is that going from lighter to the heavier chalcogens, hydrogen bonding plays a less, while chalcogen bonding an increasingly important role for the coordination of anions. Anion-pi interactions also show importance, especially for the sulfur and selenium derivatives. The noncovalent interaction modes of 2-chalcogeno-imidazolium salts have been studied in the solid state, in solution by DOSY, NMR titration and activation experiments, as well as in silico. A combined anion-pi /chalcogen bonding interaction mode prevails for most compounds. For the tellurium derivatives, the pure chalcogen bonding gains in importance, while hydrogen bonding becomes more relevant for the sulfur analogs. image