Precursor structures (PSs) in solution are expected to influenceb oth nanocrystal formation mechanisms, as well as crystallization of specific polymorphs. Herein, Group 13 PS structures determined by paird istribution functiona nd extended X-ray absorption fine structure analysis are reported.C orner-sharing octahedral dimers form from the metal nitrates dissolved in either water,i sopropanol, or ethanol at room temperature contradicting previous studies that suggested monomers or larger Keggin clusters. Because all crystalline indium oxides have octahedral coordination, crystalsc an easily nucleate from the observed PSs. Similarly,M OOH (M = Al and Ga) with octahedral Mc oordination is expected to form readily from the PSs, whereas formation of g-M 2 O 3 requires ap artial conversion to tetrahedral Mcoordination. This explains the long-standing observation of initial AlOOHf ormation as ab ottleneck for g-Al 2 O 3 synthesis. Different indium polymorphs crystallize from the variouss olvents, and thus there is no obvious link between the PSs and observed polymorphism.The Group 13 oxides are extremely important in technological applications. [1] Indeed, huge amounts of g-Al 2 O 3 are produced every month worldwide as catalyst support material, watertreatment agent, or image-enhancementa dditive, [1a, 2] whereas Ga 2 O 3 and In 2 O 3 are essential materials, for example, in the semiconductor industry. [1b,c] Al, Ga, and In form relatedo xides and hydroxides, such as M(OH) 3 ,MOOH and M 2 O 3 ,but the individual systems exhibit complex polymorphism with many different crystal structures. In general, the physicala nd chemical properties are controlled not only by the exact crystals tructure, but also the crystal morphology and size, [1a] and it is challenging to achieve control of all these characteristics. For all three systems, it is possible to calcine MOOH to form various M 2 O 3 polymorphs, but for industrial applications,i ti sd esirable to avoid the energy-consuming calcination step.M oreover,t he resultingm orphologya nd size of the M 2 O 3 crystals typically reflect the intermediate MOOH, and in addition high-temperatures fosters crystalliteg rowth, which further limits the control. Thus,d irect synthesis pathways are targeted. This wasa chieved by Lock et al. [3] andN oguchi et al. [4] who reported onestep synthesis of g-Al 2 O 3 (withint he time resolution of the experiments) at very specific solvent conditions or at very high reactiont emperature.C orrelation between the water content/ solventa nd the resulting oxide phase has also been reported for the In system. [5] However, to controla nd further develop Group13 oxide synthesis, atomics cale understandingo ft he crystal formation processes is required.During the last decade it has becomei ncreasingly clear that classical crystal nucleation theory established for supersaturated solutions [6] and homogenous melts [7] is too simplistic in relation to the complex chemical solutione nvironments presenti n formation of many modernm aterials. [8] Understan...