Rh-103 NMR parameters and the bonding structure of three complexes of [Cp*RhX2](2), where X = Cl, Br, or I, have been studied with the help of natural bond orbitals (NBOs) and natural localized molecular orbitals (NLMOs). The complexes of [Cp*RhX2](2), where X = Cl, Br, or I, have similar bonding structures, with the major difference being in the degree of covalency of the Rh-X bonds. The decomposition of Rh-103 NMR shielding into diamagnetic, paramagnetic, and spin orbit terms shows that normal halogen dependence (NHD) of the Rh-103 NMR shift is defined mostly by the paramagnetic term, with the spin-orbit term being significantly smaller. The decomposition of Rh-103 shielding into spin-free NBO and NLMO contributions shows that Rh-103 shielding is dominated by Rh d-orbital deshielding contributions. We explain the NHD of the 103(Rh) NMR shift with the increase in the energies of the virtual antibonding Rh-X orbitals along the X = Cl, Br, and I series.