The influence of interparticle contact in nanoparticle-based aerogelnetwork structures is investigated by selectively connecting or isolating the buildingblocks inside of the network, thereby coupling and decoupling them in regards to theiroptical and electronic properties. This is achieved by tuning the synthesis sequence andexchanging the point of shell growth and the point of particle assembly, leading to twodistinctly different structures as examined by electron microscopy. By thoroughexamination of the resulting optical properties of the generated structures, the clearcorrelation between nanoscopic/microscopic structure and macroscopic optical proper-ties is demonstrated. Temperature-dependent measurements and effective massapproximation calculations support ourfindings.