Complexes of metal acetylacetonate are used as general precursors for the synthesis of metal oxide nanomaterials. In the present work, we study the interaction of low-energy (<10 eV) electrons, produced abundantly as secondary electrons during the bombardment of the substrate by the primary particles, with thermally evaporated manganese(II) acetylacetonate complexes. We found that the acetylacetonate anion ([acac]−) is the major anionic species produced, while the second most abundant is the parent anion [Mn(II)(acac)2]−. This observation differs from those reported from electron attachment to Cu(acac)2, for which [Cu(II)(acac)2]− is the predominant anion [Kopyra et al. Phys. Chem. Chem. Phys. 2018, 20, 7746]. The experimental data are supported by theory to provide information on the physical-chemistry processes initiated by slow electrons to the organometallic precursor and to interpret the different behavior of Mn(acac)2 compared to Cu(acac)2.