Diffusion of piperidine and pyridine into an acidified aqueous solution of Na₂MoO₄, yield compounds [(pipH)₄][Mo₈O₂₆] · 4H₂O (pip = piperidine = C₅H₁₁N) (1) and [(pyH)₄][Mo₈O₂₆] (py =pyridine = C₅H₅N) (2), respectively. Compound 1 possesses supramolecular 3-D network and the relevant connectivity pattern generates channels of approximate dimensions of 10.76 × 11.57´A^{° 2}, in which the piperidinium cations are located as guests. Multidimensional supramolecular frameworks (3-D in compound 1 and 2-D layer type of network in compound 2) have been made possible, as the organic cations and polyoxometalate (POM) anions are glued together by significant hydrogen bonding interactions. The synthesis of compounds 1 and 2 provides a unique ‘gas–liquid’ synthetic route in POM chemistry that result in organic–inorganic hybrid materials with structural diversities. This synthetic approach, first time in POM chemistry, can be described as a potential bag filter for volatile organic amines.