3D nanoparticle assemblies offer a unique platform to enhance and extendthe functionality and optical/electrical properties of individual nanoparticles.Especially, a self-supported, voluminous, and porous macroscopic material builtup from interconnected semiconductor nanoparticles provides new possibilitiesin the field of sensing, optoelectronics, and photovoltaics. Herein, a method isdemonstrated for assembling semiconductor nanoparticle systems containingbuilding blocks possessing different composition, size, shape, and surfaceligands. The method is based on the controlled destabilization of the particlestriggered by trivalent cations (Y3+, Yb3+, and Al3+). The effect of the cations isinvestigated via X-ray photoelectron spectroscopy. The macroscopic, self-supportedaerogels consist of the hyperbranched network of interconnected CdSe/CdS dot-in-rods, or CdSe/CdS as well as CdSe/CdTe core-crown nanoplatelets isused to demonstrate the versatility of the procedure. The non-oxidative assemblymethod takes place at room temperature without thermal activation in severalhours and preserves the shape and the fluorescence of the building blocks. Theassembled nanoparticle network provides longer exciton lifetimes with retainedphotoluminescence quantum yields, that make these nanostructured materialsa perfect platform for novel multifunctional 3D networks in sensing. Various setsof photoelectrochemical measurements on the interconnected semiconductornanorod structures also reveal the enhanced charge carrier separation.