Gold nanostars are important nanoscopic tools in biophotonics and theranostics. To understand the fate of such nanostructures in the endolysosomal system of living cells as an important processing route in biotechnological approaches, un-labelled, non-targeted gold nanostars synthesized using HEPES buffer were studied in two cell lines. The uptake of the gold nanostructures leads to cell line-dependent intra-endolysosomal agglomeration, which results in a greater enhancement of the local optical fields than those around individual nanostars and near aggregates of spherical gold nanoparticles of the same size. As demonstrated by non-resonant surface-enhanced Raman scattering (SERS) spectra in the presence and absence of aggregation, the spectroscopic signals of molecules are of very similar strength over a wide range of concentrations, which is ideal for label-free vibrational characterization of cells and other complex environments. In 3T3 and HCT-116 cells, SERS data were analyzed together with the properties of the intracellular nanostar agglomerates. Vibrational spectra indicate that the processing of nanostars by cells and their interaction with the surrounding endolysosomal compartment is connected to their morphological properties through differences in the structure and interactions in their intracellular protein corona. Specifically, different intracellular processing was found to result from a different extent of hydrophobic interactions at the pristine gold surface, which varies for nanostars of different spike lengths. The sensitive optical monitoring of surroundings of nanostars and their intracellular processing makes them a very useful tool for optical bionanosensing and therapy.