The results of a study of the photoionization dynamics of iron penta-, ennea-, and dodecacarbonyl complexes are presented. In these experiments the gaseous iron carbonyl complexes are ionized via absorption of photons in the 20-90 eV energy range. Ionic products are analyzed using time-of-flight mass spectrometry. Cation pairs formed via double ionization of the iron carbonyl complexes are analyzed using photoion-photoion coincidence techniques. Photoion pairs corresponding to a direct two-body charge separation of high-mass iron carbonyl dications, such as CO+/Fe(CO)(n)(+), with n greater than or equal to 3, could not be detected. However, several ion pairs, such as C+/Fe(CO)(n)(+), with n = 0, 1, and CO+/Fe(CO)(n)(+), with n = 0, 1, have been observed generated by charge separation reactions originating from doubly charged iron carbonyl fragments. The total photoionization efficiency decreases gradually in the studied energy range between 20 and 90 eV, although a broad relative maximum in the photoionization efficiency is observed for iron pentacarbonyl around 60 eV photon energy, This relative maximum is attributed to an increased ionization efficiency caused by the iron 3p inner shell resonant excitation.