Six unusual lanthanide-transition metal compounds, [Ln2M(1,3-bdc)4(TPA)(H2O)]·nH2O (n = 2, Ln = Y, M = Co 1; n = 2, Ln = Y, M = Zn 2; n = 2, Ln = Er, M = Co 3; n = 2, Ln = Er, M = Zn 4; n = 0.5, Ln = Sm, M = Co 5) and [Y2Ni2(1,3-bdc)5(TBA)(H2O)3]·7H2O 6, where 1,3-H2bdc = benzene-1,3-dicarboxylic acid, TPA = tris(2-pyridylmethyl)amine and TBA = tris(2-benzimidazolylmethyl)amine, have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses. Compounds 1–5 are isomorphous, and crystallize in the space groupP21/c. In 1–5, the Ln atoms are connected by 1,3-bdc anions to form 2D layer structures, where the terminal M(TPA)(1,3-bdc) units are attached to both sides of the 2D layers. In compound 6, the Y atoms are connected by 1,3-bdc anions to form a 1D double chain structure. In addition, the photoluminescence and variable-temperature magnetic susceptibility of the compounds have been studied.