The crystal structures of Ni(AlCl 4 ) 2 , Ni(GaCl 4 ) 2 and Na[Ni(AlCl 4 ) 3 ] were determined by single crystal X-ray structure analysis. Ni(AlCl 4 ) 2 and Ni(GaCl 4 ) 2 are isotypic and crystallize in the Co(AlCl 4 ) 2 structure type (I2/c, a = 1276.40(9)/1268.48(7), b = 771.41(5)/757,74(3), c = 1145.47(8)/1154.34(7) pm, β = 92.067(3)/91.778(4)°, Z = 4). The structure contains chains of NiCl 6 octahedra and AlCl 4 /GaCl 4 tetrahedra linked by corners and edges. Na[Ni(AlCl 4 ) 3 ] represents a new structure type (P2 1 /c, a = 1356.34(6), b = 1200.82(6), c = 1213.31(6) pm, β = 105.647(6)°, Z = 4). Its characteristic feature is the chiral [Ni(AlCl 4 ) 3 ]− anion which is found here for the first time. The tetrachloroaluminate ions serve as bidentate ligands leading to an octahedral coordination of the nickel atom.