Abstract Crystals of two new Zintl compounds, Eu21Mn4Sb18 and Eu21Cd4Sb18 have been synthesized using the molten metal flux method, and their structures have been established by single-crystal X-ray diffraction. Both compounds are isotypic and crystallize in the monoclinic space group C2/m (No. 12, Z=4). The structures are based on edge- and corner-shared MnSb4 or CdSb4 tetrahedra, which make octameric [Mn8Sb22] or [Cd8Sb22] polyanions. Homoatomic Sb–Sb bonds are present in both structures. The Eu atoms take the role of Eu2+cations with seven unpaired 4f electrons, as suggested by the temperature-dependent magnetization measurements. The magnetic susceptibilities of Eu21Mn4Sb18 and Eu21Cd4Sb18 indicate that both phases order anti-ferromagnetically with Neel temperatures of ca. 7 K and ca. 10 K, respectively. The unpaired 3d electrons of the Mn atoms in Eu21Mn4Sb18 do contribute to the magnetic response, however, the bulk magnetization measurements do not provide evidence for long-range ordering of the Mn spins down to 5 K. Electrical resistivity measurements suggest that both compounds are narrow band gap semiconductors.