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We report the first example of an observable and reversible case of thermochromism due to the interaction of an alkylphosphonium (P6,6,6,14)+ with a β-diketonate (1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dionate-fod) of an europium(III) tetrakis-β-diketonate room temperature ionic liquid. This thermochromism is characterized by the conversion of a light yellow viscous liquid, at room temperature, to a reddish substance close to 80 °C. The reversibility of this optical effect was highlighted by the thermal stability of the Eu(III) complex.