Silicon dioxide (SiO2) has emerged as a cornerstone in the design of nano-luminescent materials owing to its exceptional chemical stability, structural tunability, and biocompatibility. This review systematically highlights the pivotal functions of SiO2 in three domains: stability enhancement, structural regulation, and function expansion. As a physical barrier, silica effectively prevents water and oxygen-induced degradation, thereby markedly improving the chemical and photostability of sensitive emitters. As a structural matrix, its mesoporous frameworks and surface chemistry enable precise loading, spatial confinement, and integration of luminescent units, while the control of pore size, defect states, and interfacial interactions allows tailoring of optical properties and energy-transfer pathways. Furthermore, advanced architectures such as core-shell, Janus, and chiral structures extend the functional boundaries of SiO2-based systems, unlocking opportunities in bioimaging, anti-counterfeiting, and smart sensing. Built on these functions, the review introduces six representative nano-luminescent materials based on silica hybrid systems (including hybrids with carbon quantum dots, inorganic quantum dots, upconversion nanoparticles, perovskites, metal nanoparticles, and organic fluorophores), and demonstrates how silica imparts stability, structural regulation, and multifunctionality for nano-luminescent materials. Finally, current challenges, such as scalable synthesis, stability under extreme environments, and potential biosafety risks, are critically discussed. We believe that a possible future direction is an integrated development strategy of "intelligent design-precise regulation-green optimization", offering theoretical and practical guidance for advancing nano-luminescent materials toward real-world applications in biomedicine, optoelectronics, and environmental monitoring.