Anderson‐type polyoxomolybdates [MMo6O18{(OCH2)3CNH2}2]3− (M = MnIII, FeIII) were prepared and structurally characterized. The tris(alkoxo) ligands are bound to the central heteroatom via their oxygen atoms. The corresponding compounds with M = NiII or ZnII are not accessible since these cations have a preference for the amino functionality. The pendant amino groups of the manganese‐containing derivative react with pyridinecarbaldehydes to give the corresponding imines. This provides new mono‐ and bidentate binding sites for metal cations.