Hydrothermal reactions of lanthanide(III) chlorides with 4-HOOC-C6H4-CH2NHCH2PO3H2(H3L) at different ligand-to-metal (L/M) ratios afforded nine new lanthanide(ill) carboxylate-phosphonates with two types of 3D network structures, namely, LnCl(HL)(H2O)(2) (Ln = Sm, 1; Eu, 2: Gd, 3; Tb, 4; Dy, 5; Er, 6) and [Ln(2)(HL)(H2L)(L)(H2O)(2)]center dot 4H(2)O (Ln = Nd, 7; Sm, 8; Eu, 9). Compounds 1-6 are isostructural and feature a 3D network in which the LnO(7)Cl polyhedra are interconnected by bridging CPO3 tetrahedra into 2D inorganic layers parallel to the be plane. These layers are further cross-linked by organic groups of the carboxylate-phosphonate liagnds via the coordination of the carboxylate groups into a pillared-layered architecture. Compounds 7-9 are also isostructural and feature a 3D open-framework composed of 1D lanthanide(III) phosphonate inorganic slabs which are further bridged by organic groups of the carboxylate-phosphonate ligands via the coordination of the carboxylate groups, forming large 1D tunnels along the b-axis which are filled by lattice water molecules. Luminescent measurements indicate that compounds 2, 4, and 5 show strong emission bands in red, green, and yellow light region, respectively. Magnetic properties of 2, 3, 5, and 7 have also been studied.