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To study the influence of heteroatoms on the photophysical properties of divalent Eu and Sr complexes, the synthesis of the phospholyl and arsolyl compounds [{(Dtp)(thf)M}2{μ-η8:η8-C8H8}] (M = EuIIand SrII; Dtp = 3,4-dimethyl-2,5-bis(tert-butyl)phospholyl) and [{(Dtas)(thf)M}2{μ-η8:η8-C8H8}] (M = EuIIand SrII; Dtas = 3,4-dimethyl-2,5-bis(tert-butyl)arsolyl) is reported. Organometallic compounds of divalent europium with P and As heterocyclic ligands have not been described previously. They were prepared by salt elimination reactions from potassium phospholyl or arsolyl, K2C8H8, and EuI2(thf)2or SrI2. Photophysical properties were investigated alongside a reference cyclopentadienyl complex with a comparable structure. Critically, the influence of the heteroatom on the photoluminescence emission and excitation and quantum yields of the complexes is significant. Density functional theory calculations were performed to rationalize the ligand influences.