Two kinds of hybrid luminescence films ([C8VIM][Eu (nta)4]@PMMA and [C8VIM][Tb (acac)4]@PMMA) have been synthesized by the copolymerization of MMA with lanthanide functionalized ionic liquid [C8VIM][Eu (nta)4]. The structure and composition of the as-synthesized films have been characterized by 1HNMR, XPS, FTIR, UV–vis, XRD, TGA and SEM. In addition, the photophysical properties of as-synthesized films have been investigated in detail by luminescence spectroscopy. It was found that the transparent and thermal stability of as-synthesized films are improved by the long chains of PMMA. More significantly, [C8VIM][Eu (nta)4] @PMMA exhibits the improvement of photo physical properties (ƞ = 52.6%) and is selected as the representative sample to examine the potential fluorescence sensing of metal ions and anions. It has been showed highly selective and sensitive fluorescence sensing for Cu2+ and CrO42−. Meanwhile, [C8VIM][Eu (nta)4]@PMMA exhibits a good stability in the aqueous solution, which is further used as fluorescence probe for detecting CO32−. The good stability, sensitive fluorescence response and good mechanical processing properties of [C8VIM][Eu (nta)4]@PMMA show a great potential to establish a fast response anion and cationic of aqueous solution fluorescence colorimetric sensor devices.