Bi₂S₃ was dissolved in the presence of NaCl in the ionic liquid [BMIm]Cl ⋅ 4AlCl₃ (BMIm=1-n-butyl-3-methylimidazolium) through annealing the mixture at 180 °C. Upon cooling to room temperature, orange, air-sensitive crystals of Na(Bi₇S₈)[S(AlCl₃)₃]₂[AlCl₄]₂ (1) precipitated. X-ray diffraction on single-crystals of 1 revealed a triclinic crystal structure that contains (Bi₇S₈)⁵⁺ spiro-dicubanes, [S(AlCl₃)₃]²⁻ tetrahedra triples, isolated [AlCl₄]⁻ tetrahedra, and sodium cations.