Spectroscopic, photochemical, and photoinitiation studies are reported for a series of monobenzoylferrocenes and 1,1＇-dibenzoylferrocenes. These nonionic metallocene complexes absorb strongly in the ultraviolet and visible wavelength regions owing to electronic transitions of mixed ligand field/charge-transfer character. Irradiation of the complexes in methanol results in ring-metal cleavage to yield a benzoyl-substituted cyclopentadienide carbanion and the corresponding half-sandwich iron(II) complex. This process occurs with an appreciable quantum efficiency (>0.30 at 546 nm) for 1,1＇dibenzoylferrocenes; in contrast, monobenzoylferrocenes are appreciably less photosensitive. When the solvent is neat ethyl alpha-cyanoacrylate, the photogenerated carbanion initiates rapid anionic polymerization of this electrophilic monomer. Several factors that can influence the performance of benzoyl-substituted ferrocenes as anionic photoinitiators are considered.