Solid polymer electrolytes based on chitosan and europium triflate were prepared by solvent casting and characterized by X-ray diffraction, scanning electron microscopy(SEM), atomic force microscopy(AFM), and photoluminescence spectroscopy. The X-ray diffraction exhibited that the samples were essentially amorphous with organized regions over the whole range of the salt content studied. The AFM analysis demonstrated that the smoother sample had roughness of 4.39 nm. Surface visualization through SEM revealed good homogeneity without any phase separation for more conductive samples and the less conductive showed some imperfections on the surface. The emission and excitation spectra displayed the characteristic bands of Eu(CF_3SO_3)_3 in addition to broad bands corresponding to the polymer host. The excited state ~5D_0 lifetime values ranged from 0.29–0.37 ms for the studied samples. Solid polymer electrolytes based on chitosan and europium triflate were prepared by solvent casting and characterized by X-ray diffraction, scanning electron microscopy (SEM), atomic force microscopy (AFM), and photoluminescence spectroscopy. The X-ray diffraction studies that the samples were essentially amorphous with organized regions over the whole range of the salt content studied. The AFM was analyzed for that the smoother sample had roughness of 4.39 nm. Surface visualization through SEM revealed good homogeneity without any phase separation for more conductive samples and the less conductive showed some The emission and the excitation spectra displayed the characteristic bands of Eu (CF_3SO_3) _3 in addition to broad bands corresponding to the polymer host. The excited state ~ 5D_0 lifetime values ​​ranged from 0.29-0.37 ms for the studied samples.