Three novel Ln(III)-based coordination polymers, {[Ln(2) (2,4-bpda)(3) (H2O)(x)]center dot yH(2)O}(n) (Ln = La (III) (1), x = 2, y = 0, Ce (III) (2), Pr (III) (3), x = 4, y = 1) (2,4-H(2)bpda = benzophenone-2,4-dicarboxylic acid) have been prepared via a solvothermal method and characterized by elemental analysis, IR, and single-crystal X-ray diffraction techniques. Complex 1 exhibits a 3D complicated framework with a new 2-nodal (3,7)-connected (4(2).5) (4(4) . 5(1) . 6(6) . 8) topology. Complexes 2 and 3 are isomorphous, and feature a 3D 4-connected (6(5) . 8)-CdSO4 network. Moreover, solid-state properties such as thermal stabilities and luminescent properties of 1 and 2 were also investigated. Complex 1 crystallized in a monoclinic space group P2(1/c) with a = 14.800 (3), b = 14.500 (3), c = 18.800 (4) angstrom, beta = 91.00 (3), V = 4033.9 (14) angstrom(3) and Z = 4. Complex 2 crystallized in a monoclinic space group Cc with a = 13.5432 (4), b = 12.9981 (4), c = 25.7567 (11) angstrom, beta = 104.028 (4), V = 1374.16 (7) angstrom(3) and Z = 4.