Among secondary metabolites produced for the selective sequestration of iron, α-hydroxy carboxylic acid containing siderophores undergo photochemical modification to enhance the bioavailability of iron. Previous works have offered limited mechanistic insight into the photodegradation of corresponding, native Fe3+ complexes. This study investigates the photoreactivity of the siderophore aerobactin and the corresponding Ga3+, Sc3+, Ti4+ and Zr4+ metal complexes in direct comparison with Fe3+. Using UV–vis spectroscopy, nuclear magnetic resonance (NMR), complemented by TD-DFT calculations, we demonstrate that ligand-to-metal charge transfer (LMCT)-driven photocleavage of aerobactin–metal complexes (Fe³⁺, Ga³⁺, Sc³⁺, Ti⁴⁺, Zr⁴⁺) results in photocleavage products that differ in dependence of excitation wavelength. Fe³⁺ complex exhibits distinct photoreactivity at wavelengths 265 nm, 320 nm, and 500 nm producing C-C bond cleavage to release CO2 and form the corresponding tautomer. However, the corresponding Ti⁴⁺ and Zr⁴⁺ complexes have LMCT bands centered at 295 nm and 285 nm, respectively, which can be selectively excited to produce the same photoproduct as the corresponding metal complex as a rare instance of xenometal-siderophore photochemistry occurring. These results experimental results paired with TD-DFT findings reveal that the terminal hydroxamate groups, rather than α-hydroxy carboxylate, are the source of efficient LMCT excitation and radical formation, challenging previous assumptions about aerobactin’s photochemical decarboxylation mechanism. These conclusions provide a mechanistic framework for siderophore-mediated photochemistry and highlight its potential for selective metal ion separation, environmental remediation, and industrial applications. Further exploration of non-native metal complexes and selective wavelength excitation may unlock new avenues for fine tuning photoreactivity.