[NBu4]3[W(CN)8] is easily accessible via the oxidation of potassium octacyanotungstate(IV) in water with nitric acid, Similar H … F contact distances of methyl groups have been observed before, for example between the methyl groups of the highly electrophilic decamethylferrocene dication and hexafluorometalate anions. In all three structures, the C≡N-Me ligands are essentially linear.