The title compound has been produced by using the radio frequency (RF) method. Barium and carbon were evaporated simultaneously under dynamic flow of helium at different temperatures. About 0.5 mg of pure Ba@C-74 was isolated via a three-step high-pressure liquid chromatography separation. For the first time, the structure of a monometallofullerene has been analyzed by means of single-crystal synchrotron diffraction on microcrystals of Ba@(C74Co)-Co-.(OEP)(.)2C(6)H(6) (Co-II(OEP): cobalt(II) octaethylporphyrin) at 100 K The monometallofullerene exhibits a high degree of localization of the endohedral metal ion, with just two split positions for Ba and two orientations of the C-74-cage. The barium atom is localized inside the C-74-cage and displaced off-center, toward the Co(OEP) molecule (d approximate to 127 pm). The shortest Ba-C distance is 265 pm. The Co(OEP) molecules form dinners in which the coordination of the cobalt is (4 + 1). Due to the all-syn conformation of the ethyl groups, each Co(OEP) molecule of the dimer coordinates one C-74-fullerene. The units (Ba@C-74)[Co(OEP)](2)(Ba@C-74) are arranged in a distorted primitive hexagonal packing. The free space between these complex units is filled by benzene molecules of crystallization. The Ba L-III XANES spectrum of a thin film sample of Ba@C-74 exhibits a pronounced double maximum structure at about E = 5275 eV. The comparison of the shape resonances of the experimental data with simulated XANES spectra, based on different exo- and endohedral structure models, confirm that the Ba. atom is located inside the C-74-cage (D-3/h) in an off-center position. The Ba. atom is shifted by about 130-150 pm from the geometric center of the C-74-cage. This is in good agreement with quantum chemical results. Thus, despite the disorder still present, a consistent and conclusive structure model for the title compound has been derived by employing a combination of X-ray diffraction, XANES spectroscopy, and quantum chemical calculations.