In this work, we have studied the structural behavior of Fluortie-type (F-type) Ce-based oxides of compositions Ln₂Ce₂O₇ (Ln = Pr, Nd and Eu). F-type oxides can be considered as multi-functional materials due to the deficiency of anions. Pr₂Ce₂O₇ (PCO), Nd₂Ce₂O₇ (NCO) and Eu₂Ce₂O₇ (ECO) were prepared by ethylene glycol-assisted sol–gel method. The structural investigation of these oxides was carried out by Powder XRD and Rietveld refinement. All the materials were found to crystallize in the cubic lattice with space group $Fm\bar{3}m$. Raman spectra of these materials are reliable with their XRD data. The morphology and bandgap energy of all the samples were obtained from SEM and KM plot, respectively. The visible light photocatalytic performance of these oxides was examined against the degradation of methylene blue under ambient conditions. The photoluminescence property of the rare earth ionswas also studied, and the color coordinates were calculated using CIE 1931 chromaticity.