Polymeric systems have played an important role as structure-directing agents and in the control of nucleation and growth of crystals. This article reviews the work of our research group in the field of the polymer-assisted crystallization of inorganic materials, mainly focused on the formation of highly ordered, porous molybdenum oxide nanostructures. Different experimental parameters including the influence of poly(ethylene oxide)-containing polymers on the morphology and structure of the products obtained from peroxomolybdate solutions are examined. Our electrochemical investigations on molybdate species are also briefly described. Finally, the importance of the precursor species in the formation of the final product is discussed.