Abstract New crystalline cobalt, nickel, zinc, and mercury halide adducts with polyethers as ligands have been isolated, characterized, and identified as [Co(μ‐Cl) 2 CoCl 2 (glyme) 2 ] (glyme = 1,2‐dimethoxyethane), cis ‐[CoI 2 (H 2 O) 2 (glyme) 2 ] 2+ [CoI 4 ] 2– , [NiI 2 (glyme) 2 ], [ZnI 2 (glyme)], [HgCl 2 (glyme)], [CoI 2 (diglyme)] (diglyme = bis(2‐methoxyethyl)ether), [ZnI 2 (diglyme)], [HgI 2 (diglyme)], [CoCl(μ‐Cl)(diglyme)] 2 , [NiI(μ‐I)(diglyme)] 2 , [Co(μ‐Cl)(triglyme)] 2 2+ [CoCl 2 (μ‐Cl)] 2 2– , and cis ‐[(NiI 2 )(triglyme)] n . These compounds were obtained from the metal halide salts in solution of glyme or diglyme, and some of them show unusual coordination numbers and arrangements.