The extraction of the solid state materials “MSnBix“ (M/x=Cs/1, Na/3) in liquid ammonia in the presence of different chelating agents yielded the novel Zintl anion [Sn5Bi3]3−. The anion could be crystallized and characterized via single crystal X-ray diffraction in [Cs@[18]crown-6]3[Sn5Bi3] ⋅ 7NH3, [K@[18]crown-6]1.5[Cs@[18]crown-6][Cs@([18]crown-6)2]0.5[Sn5Bi3] ⋅ 3.98NH3, [Na@DB[18]crown-6]2[Na(NH3)6][Sn5Bi3] ⋅ 14NH3 and [Cs@[2.2.2]crypt]6[Sn5Bi3]2 ⋅ 9.53NH3. The [Sn5Bi3]3− anion is further investigated by mass spectrometry and DFT calculations to confirm its composition and elucidate its electronic structure.