Four transition–lanthanide metal–organic coordination polymers, namely [Ag2Ln(nic)4(H2O)4·(ClO4)·H2O] [Ln=Eu (1), Gd (2)] and [AgLn(nic)2(ox)0.5(H2O)2·(ClO4)·H2O] [Ln=Tb (3), Yb (4)] (nic=nicotinate; ox=oxalate) have been synthesized by the hydrothermal reactions of 4d and 4f metal salts with N-/O-donor ligands. The isostructural complexes 1 and 2 exhibit novel 2D wave-like heterometallic layers constructed by the assembly of 1D chains of lanthanide–carboxylate with Ag(nic)2 subunits. Complexes 3 and 4 show another unusual 3D heterometallic coordination framework constructed from 2D lanthanide–oxalate layers and pillar-like Ag(nic)2 subunits. Furthermore, the luminescent properties of complexes 1 and 3 were studied.