Symmetry-breaking charge separation in molecular materials has attracted increasing attention for optoelectronics based on single-material active layers. To this end, Fe(III) complexes with particularly electron-donating N-heterocyclic carbene ligands offer interesting properties with a (LMCT)-L-2 excited state capable of oxidizing or reducing the complex in its ground state. In this Communication, we show that the corresponding symmetry-breaking charge separation occurs in amorphous films of pristine [Fe(III)L-2]PF6 (L = [phenyl(tris(3-methylimidazol-2-ylidene))borate](-)). Excitation of the solid material with visible light leads to ultrafast electron transfer quenching of the (LMCT)-L-2 excited state, generating Fe(II) and Fe(IV) products with high efficiency. Sub-picosecond charge separation followed by recombination in about 1 ns could be monitored by transient absorption spectroscopy. Photoconductivity measurements of films deposited on microelectrode arrays demonstrated that photogenerated charge carriers can be collected at external contacts.