Luminescent colloidal silicon quantum dots (SiQDs) are sustainable alternatives to metal-based QDs for various optical applications. While the materials are reliant on their photoluminescence efficiency, the relationship between the structure and photostability of SiQDs is yet to be well studied. An amorphous silicon (a-Si) shell was recently discovered in SiQDs prepared by thermally-processed silicon oxides. As a-Si is known as a source of defects upon UV irradiation, the disordered shell could potentially have an adverse effect on the optical properties of nanoparticles. Herein, the photostability of ∼5 nm diameter SiQDs with an amorphous shell was compared with that of over-etched SiQDs of equivalent dimensions that bore an a-Si shell of negligible thickness. An UV-induced degradation study was conducted by subjecting toluene solutions of SiQDs to 365 nm light-emitting diodes (LEDs) under an inert atmosphere for predetermined times up to 72 hours. The structure, composition, and optical responses of the exposed SiQDs were evaluated.