Today the high potential of (organo)silica branched/crosslinked/network polymers in nanofibrous membranes cannot be exploited to the fullest due to the lack of a straightforward way to produce them. To solve this, a fundamental understanding of how sol-gel synthesis and electrospinning are related via rheology is required. The main bottleneck remains that the viscosity evolution, as the network develops during synthesis, cannot be fully interpreted at the molecular level. For this, it is essential to fundamentally link the different steps in the electrospinning production process: from network formation of (organo)silica precursor molecules over electrospinning toward nanofibrous membranes. Both experimental (e.g. 29Si NMR, rheology) and kinetic modelling techniques will be used for this purpose. The morphology of the resulting nanofibrous membranes will be determined and linked back to the chemical building blocks, sol-gel synthesis and the electrospinning process as to enable the tuning of these (organo)silica nanofibers for advanced applications. The fiber diameter and the wettability will be studied as key model properties at respectively the fiber and material membrane level. This generic methodology can in the future be expanded toward other material properties to allow for molecular scale-driven material property tuning.