AbstractThe knowledge advancement in the physics of silicon dioxide has promoted ground-breaking progress, from microelectronics to fibre optics. However, the SiO₂ exciton decay mechanism is still mostly unrevealed. Here, we analyse the temperature dependence of interband-excited luminescence and the reflectivity by means of synchrotron radiation on a wide selection of SiO₂ materials. This enables us to decouple the band-to-band recombination steps from non-radiative decay pathways that typically mask the relaxation mechanisms. We show that band-to-band excitations decay into two competitive correlated channels leading to green and red luminescence so far ascribed to independent transitions. Here we discuss the assignment to a dual relaxation route involving either ‘free’ or ‘interacting’ non-bridging-oxygen sites. Such an interpretation suggests an explanation for the elusive non-bridging-oxygen centres in quartz. The reflectivity spectra finally demonstrates a general relationship between exciton spectral position and bandwidth in SiO₂ and clarifies the role of disorder in exciton localization.