The spectroscopic characteristics (excitation, emission and lifetime) of EuIII dissolved in 1‐methyl‐3‐butylimidazolium bis(trifluoromethanesulfon)imide (BumimTf2N) are reported. In a first series of experiments, the effect of the presence of water in BumimTf2N was examined. It appears that non‐degassed solutions are most probably inhomogeneous, displaying large water clusters leading to an intense diffusion of the red light of an He:Ne laser. In these samples, the Eu emission spectrum is close to that observed in slightly acidic aqueous solutions. In contrast, when the samples were degassed the solution appeared homogeneous and water can be considered as a competitive ligand for the first coordination sphere of Eu. In a subsequent series of experiments, tetrabutylammonium chloride (TBACl) was added to the solution and the resultant species investigated. The ensuing enhancement in the metal‐centered luminescence has been interpreted in terms of changes in the inner coordination sphere of the EuIII ion and possible structures are discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)