A method was developed for the low-temperature sol–gel synthesis of one of the most popular components of functional and structural materials — nanostructured yttrium aluminum garnet Y3Al5O12 — using precursors from the class of alkoxoacetylacetonates produced from the corresponding acetylacetonates. It was determined that increasing duration of heat treatment of yttrium-aluminum-containing xerogen in air to 6 h reduces the crystallization temperature of the Y3Al5O12 phase from 920 – 930 to 750 – 800°C, which was confirmed by IR spectroscopy and X-ray powder diffraction analysis. The microstructure of nanocrystalline yttrium aluminum garnet obtained at 800°С was studied; it was found that the size of crystallites is 30–40 nm, the size of particles is 30–50 nm, and the size of pores is 20–30 nm. Small-angle neutron scattering demonstrated that, in the powders synthesized at 700–800°C, there is structural ordering of the short-range type, whereas in the nanocrystalline samples heat-treated at a higher temperature (850°С), there is no such ordering.