We describe the role of chalcogen variation (O, S, Se and Te) on the photoluminescence properties of ether-based luminophores showing aggregation-induced fluorescence and phosphorescence. To this end, a library of eleven different compounds with varying substitution patterns was synthesized and analyzed in terms of their photophysical properties. Ortho-and tetraselenoethers revealed remarkable phosphorescence properties. To the best of our knowledge, these are one of the first phosphorescent organic selenium-containing compounds fea-turing AIE properties. Besides photophysical investigations, Xray diffractometric analyses were performed, yielding the molecular structures of nine compounds in a crystalline environment, facilitating a direct correlation between the packing and the emission performances. All experimental results were supported by quantum chemical calculations providing an in-depth understanding of the role of chalcogens within this class of compounds.