The rhodium complex Rh(HL)(COD)Cl, 1, L being a functionalized N-heterocyclic carbene (NHC) ligand with an oxygen-containing pendant arm, has been used as the entry point to synthesize a series of neutral and cationic Rh(I) O,C chelates. While the Rh–carbene interaction is similar in all these 16-electron complexes, structural analysis reveals that the strength of the Rh–O bond is greatly affected by the nature of the O-donor: R-O⁻ > R-OH > R-OBF₃. These subtle changes in the nature of the O-containing tether are found to be responsible for large differences in the alkene hydrosilylation catalytic activity of these compounds: the stronger the Rh–O interaction, the better the catalytic performances. The most active catalyst, [Rh(L)(COD)], 2, demonstrated good catalytic activity under mild reaction conditions for the hydrosilylation of a range of alkene substrates with the industrially relevant non-activated tertiary silane, 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD^HM). Furthermore, this complex is an effective catalyst for the selective remote functionalization of internal olefins at room temperature via tandem alkene isomerization–hydrosilylation.