The influence of three prototypic families of bridging ligands (carboxylate, carboxamidate, and ortho-metalated arylphosphines) on the electronic structure of dirhodium(II) carbene complexes was theoretically analyzed. The calculations indicated that the electron donation of the ligand to the Rh atom, rather than the chelating ability or the metal-ligand orbital mixing, was responsible for tuning carbene charge via back-donation, which can influence the reactivity and selectivity of the dirhodium complexes in catalytic carbene transfer reactions.