Complexes of rhodium(II) acetate with 2H-azirines were obtained for the first time. The 1 : 2 complexes were characterized using 1H and 13C NMR, IR, and UV spectroscopy and high-resolution mass spectrometry. The structure of Rh2(OAc)4 complex with two 3-(4-methoxyphenyl)-2H-azirine molecules was studied by X-ray diffraction analysis. In crystal, the molecule of this complex belongs to the Ci point group.