Specific ion-molecule reactions are used to prepare two intermediates of the FeO++CH4 reaction, and photodissociation of the jet-cooled intermediates is examined in the visible and near-ultraviolet using time-of-flight mass spectrometry. The photodissociation spectrum of the aquo iron carbene complex [H2C=Fe-OH2](+) shows transitions to at least four excited electronic states in the FeCH2+ chromophore, with broad vibrational structure. Photoexcitation of the insertion intermediate [HO-Fe-CH3](+) leads to formation of FeOH++CH3 and also triggers the reaction to produce Fe++CH3OH. The photodissociation spectrum of [HO-Fe-CH3](+) presents a vibrationally resolved band involving progressions in the excited state Fe-C stretch, Fe-O stretch, and O-Fe-C bend. The change in the Fe-C bond length in [HO-Fe-CH3](+) and [H2C=Fe-OH2](+) upon photoexcitation is calculated from a Franck-Condon analysis of the vibronic features observed. The analysis of the experimental results is aided by hybrid Hartree-Fock/density-functional (B3LYP) calculations on [HO-Fe-CH3](+) and [H2C=Fe-OH2](+) performed to determine molecular parameters, and time-dependent density functional theory (TD-DFT) calculations on FeCH2+ to predict excited electronic states.