Four isostructural transition metal-based MIL-53 anologues, [M(ntd)(e-urea)] (M = Mn, 1; Co, 2; Zn, 3; Cd, 4; ntd = 1,4-naphthalenedicarboxylate; e-urea = ethyleneurea), are urothermally synthesized and structurally characterized by single crystal X-ray diffraction, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), elemental analysis (EA) and Infrared Spectroscopy (IR). The results of TGA and PXRD for these isostructural compounds show that they exhibit distinct thermal behaviors, where the Zn- and Cd-forms are much easier to lose the ligated e-urea molecules from the frameworks than the Mn- and Co-forms. The CO 2 sorption properties and photoluminescent properties of compounds 3 and 4 were also investigated.