Separation processes based on room temperature ionic liquids (RTIL) and electrochemical refining are promising strategies for the recoveryo fl anthanides from primary ores and electronic waste. However,t hey require the speciation of dissolved elements to be knownw ith accuracy. In the present study,E uc oordination and Eu III /Eu II electrochemical behavior as af unction of water contenti n1-ethyl-3methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm] [NTf 2 ]) was investigatedu sing UV-visible spectrophotometry, time-resolvedl aser fluorescence spectroscopy,e lectrochemistry,a nd X-ray absorption spectroscopy. In situ measurements were performed in spectroelectrochemicalc ells. Undera nhydrous conditions, Eu III and Eu II were complexed by NTf 2 ,f orming EuÀOa nd EuÀ(N,O) bonds with the anion sulfoxide functiona nd Na toms, respectively.T his complexation resulted in agreater stabilityofEu II ,and in quasi-reversible oxidation-reduction with an E 0 'p otential of 0.18 V versust he ferrocenium/ferrocene (Fc + /Fc) couple. Upon increasingw ater content,p rogressivei ncorporation of water in the Eu III coordination sphereo ccurred. This led to reversible oxidation-reduction reactions, but also to ad ecreasei n stabilityo ft he + II oxidation state (E 0 ' = À0.45 Vv s. Fc + /Fc in RTIL containing 1300 mm water).