An unusual thermally sensitive anion-cation interaction, which is characteristic of the anion [Eu(FOD) ] , occurs in the complex [CHOL][Eu(FOD) ] (1; CHOL=choline; FOD=1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate) and affects both quantum yield and thermochromic behavior. This prompted the design of an Eu -based ratiometric thermometer that functions at temperatures up to 95 °C through a thermally excited state absorption of the Eu ion. The reusable temperature-sensitive luminescent complex showed a range of relative sensitivity between 0.45 % C at 25 °C, with an increase to 7.0 % C at 95 °C. Confinement of compound 1 in a transparent film of polysulfone resulted in a higher thermal stability of 1 while its luminescence showed a strong temperature dependence.