Two novel homochiral lanthanide-silver heterometallic coordination polymers LnAg(OAc)(IN)(3) [Ln = Nd (1), Eu (2), HIN = isonicotinic acid, HOAc = acetic acid] have been prepared under hydrothermal conditions, which were characterized by elemental analysis, infrared, thermogravimetric analysis, and single-crystal X-ray diffraction. Both complexes are isostructural and crystallize in a hexagonal system, chiral space group P6(1)22. Both polymers are constructed from infinite right-handed homochiral helical chains with Ln-O-Ag connectivity, representing the first examples of homochiral lanthanide-transition metal heterometallic coordination polymers with a 3D coordination framework based on spontaneous resolution. Furthermore, the luminescent properties of 2 were studied.