Two series of Pb(II)-Ln(III) heteronuclear coordination complexes are assembled from a tripodal ligand triCB-NTB ((4,4',4''-(2,2',2''-nitrilotris(methylene)tris(1H-benzo[d] imidazole-2,1-diyl)tris(methylene))tribenzoic acid). In Pb2LnL2 series, the Ln3+ ion is encapsulated in highly symmetrical {LnO6} octahedron with an inversion center, and Pb-Ln-Pb clusters are formed by the linkage of carboxyl groups on triCB-NTB ligands to Pb2+ and Ln3+ simultaneously. While in PbLn2L2 series, the Ln3+ ion is encapsulated in a distorted {LnO9} polyhedron without inversion center. Pb2+ ions are coordinated with benzimidazole and apical N atoms on the ligand isolatedly, and the carboxyl groups only link two Ln3+ ions into Ln-Ln cluster. This structural variation leads to different photoluminescence behaviour in these two series of complexes. Most importantly, the linkage of Pb-Ln-Pb clusters brings more perturbation to the excited states of the ligand. Therefore, more obvious ligand-to-metal charge transfer (LMCT) process is observed in Pb2LnL2 series, and the energy transfer to the accepting levels of Ln3+ ions becomes more efficient. Furthermore, the combination of LC (ligand-centered)+LMCT+MC (metal-centered) emissions in complex Pb2EuL2 results in single component white light emission.