We report the facial synthesis of Eu-doped MIL-53(Fe) elongated hexagonal dipyramid by solvothermal reaction of Fe(NO₃)₃, Eu(NO₃)₃ and terephthalic acid (TPA) in the presence of N,N-dimethylformamide (DMF). The as-synthesized samples were characterized by XRD, Raman, FT-IR, PL, and SEM. From XRD and Raman results, metal replacement (Eu) with the metal ion (Fe) in the crystal lattice may change the high crystallinity of the MIL-53(Fe) structure, and all the metal ions were incorporated into the structures of MIL-53(Fe) as well as replaced Fe ion or located at interstitial site. From PL result, Eu-doped MIL-53(Fe) showed unique Eu fluorescence properties with high emission intensity, thus enabling it to be a promising functional probe for fluorescent imaging.