Molecular complexes between alpha-Keggin polyanions and tetraphenylporphyrinato Zn(II) are unexpectedly stable have been obtained in the presence of an ancillary donor anion such as a halide. X-ray structure determination reveals integrated organic-inorganic stacks with alkyl ammonium cations acting as spacers. Development of these compounds, which combine thermally and photochemically redox active units, may lead to molecular materials with interesting electro-and photochromic properties.