Abstract Two organic–inorganic hybrid compounds based on amantadines and polyoxometalates formulated as (C 10H 18N) 4(H 2V 10O 28)·2DMF·2H 2O ( 1) and (C 10H 18N) 3(PMo 12O 40) ( 2), were synthesized and structurally characterized by elemental analysis, single-crystal X-ray diffraction analysis, IR, UV and TGA. Compounds 1 and 2 consist of protonated amantadines together with different polyoxometalates, [H 2V 10O 28] 4− and [PMo 12O 40] 3−, respectively. There are hydrogen bonding interactions and electrostatic attractions between polyoxometalates and amantadines in 1 and 2. Polyoxometalates are linked through amantadines into a two-dimensional network via hydrogen bonds in the two compounds. The two-dimensional framework is further extended into supramolecular network by hydrophobic interaction of amantadines between adjacent layers. The crystal packing patterns of the two compounds reveal various supramolecular framework.