Glass photonics are widespread, from everyday objects around us to high-tech specialized devices. Among different technologies, sol–gel synthesis allows for nanoscale materials engineering by exploiting its unique structures, such as transparent glass-ceramics, to tailor optical and electromagnetic properties and to boost photon-management yield. Here, we briefly discuss the state of the technology and show that the choice of the sol–gel as a synthesis method brings the advantage of process versatility regarding materials composition and ease of implementation. In this context, we present tin-dioxide–silica (SnO2–SiO2) glass-ceramic waveguides activated by europium ions (Eu3+). The focus is on the photorefractive properties of this system because its photoluminescence properties have already been discussed in the papers presented in the bibliography. The main findings include the high photosensitivity of sol–gel 25SnO2:75SiO2 glass-ceramic waveguides; the ultraviolet (UV)-induced refractive index change (Δn ~ −1.6 × 10−3), the easy fabrication process, and the low propagation losses (0.5 ± 0.2 dB/cm), that make this glass-ceramic an interesting photonic material for smart optical applications.