Material nucleation processes are poorly understood; nevertheless, an atomistic understanding of material formation would aid in the design of material synthesis methods. Here, we apply in situ X-ray total scattering experiments with pair distribution function (PDF) analysis to study the hydrothermal synthesis of wolframite-type MWO₄ (M : Mn, Fe, Co, Ni). The data obtained allow the mapping of the material formation pathway in detail. We first show that upon mixing of the aqueous precursors, a crystalline precursor containing [W₈O₂₇]^6- clusters forms for the MnWO₄ synthesis, while amorphous pastes form for the FeWO₄, CoWO₄ and NiWO₄ syntheses. The structure of the amorphous precursors was studied in detail with PDF analysis. Using database structure mining and an automated modelling strategy by applying machine learning, we show that the amorphous precursor structure can be described through polyoxometalate chemistry. A skewed sandwich cluster containing Keggin fragments describes the PDF of the precursor structure well, and the analysis shows that the precursor for FeWO₄ is more ordered than that of CoWO₄ and NiWO₄. Upon heating, the crystalline MnWO₄ precursor quickly converts directly to crystalline MnWO₄, while the amorphous precursors transform into a disordered intermediate phase before the crystalline tungstates appear. Our data show that the more disordered the precursor is, the longer the reaction time required to form crystalline products, and disorder in the precursor phase appears to be a barrier for crystallization. More generally, we see that polyoxometalate chemistry is useful when describing the initial wet-chemical formation of mixed metal oxides.