Although aerogels prepared by the colloidal assembly of nanoparticles are a rapidly emerging class of highly porous and low-density materials, their ambient dried counterparts, namely xerogels, have hardly been explored. Here we report the use of nanoparticle-based BaTiO3 xerogels as green bodies, which provide a versatile route to ceramic materials under the minimization of organic additives with a significant reduction of the calcination temperature compared to that of conventional powder sintering. The structural changes of the xerogels are investigated during ambient drying by carefully analyzing the microstructure at different drying stages. For this purpose, the shrinkage was arrested by a supercritical drying step under full preservation of the intermediate microstructure, giving unprecedented insight into the structural changes during ambient drying of a nanoparticle-based gel. In a first step, the large macropores shrink because of capillary forces, followed by the collapse of residual mesopores until a dense xerogel is obtained. The whole process is accompanied by a volume shrinkage of 97% and a drop in surface area from 300 to 220 m2 g-1. Finally, the xerogels are sintered, causing another shrinkage of up to 8% with a slight increase in the average pore and crystal sizes. At temperatures higher than 700 °C, an unexpected phase transition to BaTi2O5 is observed.