Density functional theory (DFT) and zeroth-order regular approximation DFT calculations were performed to investigate the electronic structures and C-13 and Pb-207 nuclear magnetic resonance (NMR) chemical shifts of metal-coordinated plumboles, namely, mono-rhodioplumbole ([Rh-plumbole](-)), dirhodioplumbole (Rh-2-plumbole), and dilithioplumbole (Li-2-plumbole), which have a five-membered ring containing lead. The molecular orbital correlation diagram and extended transition state-natural orbitals for chemical valence analysis of the [Rh-plumbole](-) and Rh-2-plumbole complexes showed that the plumbole is primarily a ir-donor, with Jr-donation being dominant in the Rh-2-plumbole complex. The present calculations show that the Pb-C, internuclear distances are longer in the Rh-2-plumbole complex than in [Rh-plumbole](-)because of the combined effect of strong pi-donation and weak pi-back-donation in the Rh-2-plumbole complex. The calculated Pb-207 and C-13(alpha) NMR chemical shifts agree with the experimental trends reasonably well. The influences of the relativistic effect, role of the functional, effect of the solvent, and dependence of the exact exchange admixture on the calculated Pb-207 and C-13(alpha) NMR chemical shifts were investigated. The NMR chemical shift trend of the Pb-207 atom in the complexes originates from the paramagnetic and spin-orbit contributions. NMR component analysis revealed that the upfield shift of the C-13(alpha) atoms of the [Rh-plumbole](-) and Rh-2-plumbole complexes compared to that of the Li-2-plumbole complex is mainly due to the decrease in the paramagnetic term.