Five new lanthanide complexes based on tetrazole-1-acetic ligand and 2,2′-bipyridine as auxiliary ligand have been solvothermally synthesized with the formulas [Ln 2 (1-tza) 2 (NO 3 ) 4 (2,2′-bipy) 2 ] [Ln = Nd (1), Sm (2), Eu (3), Tb (4), Dy (5), 1-tza = tetrazole 1-acetic and 2,2′-bipy = 2,2′-bipyridine] and structurally characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. The single-crystal X-ray diffraction data reveal that complexes 1–5 are dinuclear structures constructed by nitrate-O-bridged and μ 1,3 carboxyl groups from 1-tza ligand, in which each nine-coordinated center Ln(III) ion is in a slightly distorted capped square antiprism geometry. The magnetic behaviors of 1–5 have been investigated. The solid-state photoluminescent measurements illustrate that complexes Eu 3 and Tb 4 display the strong fluorescent emissions in the visible region, whereas Nd 1 shows the characteristic near-infrared(NIR) luminescence. In addition, thermogravimetric analysis of Eu 3 is also described.