Four novel three-dimensional (3D) 4d-4f heterometal-organic compounds, [LnCd(2)(Pbc)(4)(Meimdc)-(H2O)]center dot 3H(2)O (Ln = Eu, 1a; Tb, 1b; Sm, 1c; Dy, 1d) (HPbc = 4-(4-pyridinyl)benzoic acid; H(3)Meimdc = 2-methyl-1H-4,5-imidazole-dicarboxylic acid), have been successfully prepared by a hydrothermal method. All the compounds are isostructural and show three-dimensional microporous pillar layered structures with uncoordinated carboxylate sites hung in the channels. Compound 1a possesses excellent chemical stability. The luminescent investigations show that compounds 1a, 1b, 1c, and 1d display the characteristic emission bands of Ln(3+) ions. Compound la exhibits a good potential as a luminescent sensor material for multi-responsive Ag+, Cu2+, Zn+, Co2+, and Ni2+ cations and some organic amines. Interestingly, la can capture Ag+, Cu2+, Zn+, Co2+, and Ni2+ cations and shows cation-dependent colorimetric response, which indicates the potential for naked sensing.