The predictive hydrothermal synthesis of polyoxometalates (POMs) is an important challenge for their targeted production and for the design of new POM motifs and organic−inorganic POM materials. In this context, the systematic fluorination of POMs remains to be fully explored. Therefore, the structure-directing influence of cation pairs on the primary and secondary structure of polyoxofluoromolybdates(VI) is explored in the present study. In the first step, new types of mixed alkali difluorooctamolybdates ((M, M′)Mo8O26F2·nH2O; M, M′ = K−Cs) illustrate how the choice of the alkali cations controls the resulting structure type. This structure-directing potential of the cations is investigated in terms of electrostatic calculations. The concept of cation pairs as structural “spacers” and “scissors” is then applied to construct new secondary structures from the recently discovered [Mo6O18F6]6− and [Mo7O22F3]5− fluoromolybdate anions. The use of selected bicyclic organic cations (asn = 1-azoniaspiro[4,4]nonane; adu = 1-azonia-4,9-dioxaspiro[5,5]undecane) led to the new organic−inorganic fluoromolybdates asn2Na4Mo6O18F6·6H2O, adu3Na3Mo6O18F6·3H2O and adu4NaMo7O22F3·4H2O. The steering effect of the organic cations in the formation of the layered organic−inorganic structures is compared for all three compounds with respect to their potential as building blocks for constructing POM-based materials.