The photochemistry of a gas-phase complex, Mg.+(2-fluoropyridine), has been studied in the spectral range of similar to230-440 nm with a molecular beam coupled with a time-of-flight mass spectrometer. Surprisingly rich chemistry has been observed. Aside from the evaporative photofragment, Mg.+, an abundant photoproduct, C4H4.+, is observed after the electronic excitation of Mg+. The formation of this photoproduct is associated with the loss of a stable species, CN-Mg-F. Also identified in this work are reactive pathways that occur with the elimination of HCN, HF, or MgF from the complex. The observed photoreactions have been examined in detail using quantum mechanics methods. A distinct structural feature of the complex is the direct attachment of Mg.+ to the N atom of fluoropyridine due to the strong electrostatic interaction. The key to the rich photochemistry is the formation of the FMg+(C5H4N) intermediate, through facile fluorine migration. Plausible photoreaction mechanisms have been proposed. These mechanisms account for the evolution of the energized complex with the pre-defined structure en route to the target photoproducts that we have detected.