Rigid and stable networks composed of litchi-shaped microspheres were formed via hierarchical self-assembly (SA) of oxide-based nanoparticles (NPs). The phenomenon of the apparent changes from NPs networks to microspheres networks after the gelation was similar to normal microsyneresis. However, in-situ composition evolution results indicate that the SA is driven by interparticle dehydration, but not affinity difference between the network for itself and for the solvent. In-situ small-angle X-ray scattering (SAXS), UV-vis-NIR, and electric conductivity were used to study the microsyneresis process. To further demonstrate the mechanism, extra complexant was added and successfully restrained the NPs-microsphere transition by inactivating the surface hydroxyl of the NPs. Considering the structural similarity, this work may provide a new approach to control the assemblies of diverse oxide-based NPs.