The clusters Ti(6)O(4)(OPr)(8)(OOC(CH(2))(2)C[triple bond]CH)(8) and [Zr(6)O(4)(OH)(4)(OOC(CH(2))(3)C[triple bond]CH)(12)](2) with acetylenic carboxylate ligands were prepared and structurally characterized in solution and in the crystalline state. Model reactions showed that they are suitable candidates for the formation of cluster-based inorganic-organic hybrid materials by alkyne-azide click reactions.