We have measured the electron injection kinetics of four rhenium-bipyridine complexes (Re1C, ReEC, Re1TC, and Re2TC) on TiO2 nanocrystalline films using transient infrared spectroscopy. The self-assembled monolayer formation of these complexes was characterized by UV-visible spectroscopy, infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy. These complexes bind to the TiO2 surface through the formation of carboxylate groups, and these self-assembled layers are approximately a monolayer. The kinetics studies address the effect of insulating and conjugated spacers and the length of conjugation on the electron-transfer process. The insulating bridge leads to a slower injection rate and poorer injection yield compared with the conjugated spacers. The electron injection of Re2TC was found to be a fast, high-yielding, and multiple electron injector process. The ground and electronically excited states of the dye complexes were characterized using ground-state and time-dependent density functional theory. We present the role of electronic conjugation in modulating electron injection using a combination of computational and experimental work and find that these metal-based complexes adsorbed on a semiconductor surface can be used to read out the electron injection kinetics through tailored molecular bridges.