SiO2 and related dielectrics are basic constituents of many optical and electronic devices with applications in frontier optoelectronics as well as in many radiation and harsh environments. The ongoing activity of researchers ranges from fundamentals of the electron processes, including defects formation and radiation-matter interaction; to growth mechanisms, spanning from bulk to fibers, nanostructures and composites; to characterization techniques and to modeling, simulation, and devices. This issue contains 24 articles selected from the contributions to the International Symposium SiO2, Advanced Dielectrics and Related Devices, held on June 11–13, 2018 in Bari, Italy. It was the XII edition of a symposium with French-Italian organizing committees which brought together more than 60 researchers from all around the world. The collected contributions cover the different research activities of the symposium community highlighting the recent advancements and perspectives together with the forefront topics. The four feature articles span from SiO2 optical fibers where radiation, temperature and doping are shown to be critical for applications, to graphene transferred to SiO2, evidencing the relevant role of the dielectric substrate in affecting the electronic properties of the 2D material. The other frontier topics concern attractive applications of photonic and plasmonic integrated cavities in the field of biosensing and trapping of biological matter at the nanoscale as well as novel computational models for simulating electromagnetic pulse propagation into dielectrics enabling the prediction in applicative tasks. The original papers can be grouped in hot topics of defects characterization and formation in crystalline and amorphous SiO2 with reference also to F, Bi, Al, P, Gd and other dopants of recent and avant-garde interest for applications, considering both experimental and simulative studies. In addition, many optical devices including sensors, optical fibers and waveguides have been reported evaluating both their stability and performances. Finally, nanostructures, ceramics and composites system based on SiO2 have been deepened with perspective to applications in emerging fields as solar energy, healthcare and environment. We kindly acknowledge all the authors and the reviewers for their contribution and the Journal Physica Status Solidi (a) for acceptance to publish this special issue. The editor's continuous support during all the publication steps has been indispensable for the final goal. The SiO2 Symposium is one of the best forums to meet and exchange ideas in the physics and chemistry of SiO2 and novel dielectrics. Finally, we would like to dedicate this issue to Roberto Boscaino, passed away this year. On behalf of the scientific community we express our deepest respect for him: for both what has he done himself directly in Physics and, in particular, for the enormous and successful work done in developing his research group, teaching, supporting and encouraging his collaborators. Together with Italian and French colleagues, Roberto Boscaino has fully promoted the SiO2 Symposium and created a strong international momentum in SiO2 studies. Organizing committee Luciano Mescia (Chair) Marco Cannas (Chair) Simonpietro Agnello Franco Mario Gelardi