© 2020 American Chemical Society. Enormous efforts have been devoted to the development of crystalline aerogels toward heterogeneous catalysis, energy storage, ion/molecular absorption, and luminescence. However, properties of aerogels are not fully exploited due to their low content of functional moieties embedded in their solid networks, low crystallinity, and limited chemical compositions. Herein, we develop a one-pot approach based on crystallization from amorphous metal hydroxides modified with a β-diketone ligand, toward crystalline transition-metal hydroxide aerogels. Synthesis of monolithic and crystalline aerogels of layered double hydroxide (LDH) was performed in a Ni-Al system starting from aqueous ethanol solutions of NiCl2·6H2O and AlCl3·6H2O with acetylacetone (acac) as an organic ligand. Propylene oxide (PO) as an alkalization reagent was added into precursory solutions to yield monolithic wet gels. The successive pH increase induces the formation of a three-dimensional (3-D) solid framework composed of amorphous Al(OH)3. Then, amphoteric Al(OH)3 undergoes crystallization into Ni-Al LDH via an acetylacetone-driven dissolution-crystallization of metal hydroxides without destroying the preformed 3-D solid framework. The process allows us to obtain crystalline aerogel monoliths with high porosity and high transparency after supercritical CO2 drying of wet gels. The present scheme can be expected to synthesize functionalized aerogel composed of crystalline transition-metal oxide/hydroxide nanobuilding blocks (NBBs).