Resonant inelastic X-ray scattering spectra at the iron L-edge from hemin in dimethyl sulfoxide liquid solution are reported. Our experiments, which are interpreted with the help of electronic structure calculations, support earlier assignments of hemin-solvent interactions, including the iron spin state and the role of the chloride ligand obtained from a total fluorescence yield study. The analysis of the explicit radiative relaxation channels of 2p core-level excited iron, explored in the present work, allows for a rather quantitative assignment of the orbitals involved in the excitation-deexcitation process of the core-excited hemin in solution. We specifically distinguish between contributions of partially and fully occupied valence orbitals to the broad X-ray emission band. In addition, our calculations reveal a detailed picture of the character of these orbitals.