The complexes [Et2H2N]+2[ZrCl6]2- (1), [Me3NCH2Ph]+2[ZrCl6]2-•MeCN (2), [Ph3PC6H4(CHPh2-4)]+2[ZrCl6]2-•2 MeCN (3), and [Ph4Sb]+2[ZrCl6]2- (4) were synthesized by the reaction of zirconium tetrachloride with tetraorganylammonium, -phosphonium, and -stibonium chlorides in acetonitrile and structurally characterized. The nitrogen, phosphorus, and antimony atoms in the cations have a distorted tetrahedral geometry. The Zr-Cl distances in the centrosymmetric octahedral [ZrCl6]2- anions of complexes 1-4 have similar values, the longest bonds being observed in the anion of complex 4. Acetonitrile molecules are involved in the structural organization of the crystals of complex 3 via weak hydrogen bonding with phenyl hydrogen atoms of the organylphosphonium cations. In the crystal of 2, no hydrogen bonds between the cations and solvent molecules are observed; acetonitrile molecules fill the cavities formed by cations and anions.