The reduction of tungsten hexachloride with iron powder or cobalt powder resulted in the formation of MW2Cl10 (M = Fe and Co) in fused silica tubes at 250 °C and 225 °C, respectively. Crystal structures of the new compounds were refined isotypically from X-ray powder diffraction patterns [C2/c, Z = 4, a = 6.1226(1) Å, b = 16.7943(1) Å, c = 12.3737(1) Å, and β = 108.99(1)° for FeW2Cl10, and a = 6.111(1) Å, b = 16.696(1) Å, c = 12.384(1) Å, and β = 108.97(1)° for CoW2Cl10]. The structures of Fe1/5W2/5Cl2 and Co1/5W2/5Cl2 can be considered as a cation-deficient CdI2-type structure, in which bioctahedral [W2Cl10]n– anions with n ≈ 2 introduce significant distortions. The compounds MW6Cl14 (M = Fe and Co) were prepared following the same procedure at 475 °C. Their crystal structures were refined isotypically [Pn3, Z = 4, a = 12.567(1) Å for FeW6Cl14, and 12.525(1) Å for CoW6Cl14] to the structure of PbMo6Cl14 from X-ray powder diffraction patterns.