Over recent decades, numerous studies have highlighted the importance of opal, chalcedony and quartz varieties, chiefly in volcanic, but also in metamorphic and sedimentary environments. The focus is to define accurately their structures, composition and properties, as well as to identify the factors controlling the formation and the ageing of different forms of silica. In the field of archaeological sciences efficient discriminants are the bases from which the origin and provenance of materials may be traced. Substantial efforts were made in the attempt to combine geochemical, mineralogical, petrographic and geological features with archaeological and archaeometric information. However the results show that data integration is complicated, and several unanswered questions remain. On the one hand, archaeological research has focused on technological and ethnographic aspects, mainly concerning use-wear and heat-treatment studies. Mineralogical characterization has often been limited to the identification of the material, frequently by Raman microspectroscopy alone. On the other hand, the Earth sciences have provided basic mineralogical, crystal-chemical and geological knowledge, but failed to provide a systematic data collection of sources and their geochemistry. As a consequence, large gaps persist in the identification of archaeological opals, chalcedonies and quartz varieties, and in the geographic mapping of possible sources. In this context, the present review aims to summarize the current academic debate on such issues, possibly to encourage further work in the field. After a brief introduction to terminology, the structure of opals, their colours and properties are discussed, followed by an introduction to silica dissolution/precipitation and opal-formation processes. The next section reviews the information available on use of opals and provenance from historical sources, mainly Pliny the Elder, followed by a short list of ancient and modern opal supply areas, together with a (necessarily incomplete) summary of the geological and geochemical information. The discussion then encompasses chalcedony, agate and chalcedony varieties (carnelian, sard, onyx, sardonyx, chrysoprase, Cr-chalcedony, ‘gem silica’ or ‘chrysocolla chalcedony’ and heliotrope), following the same scheme as was adopted for opals. Terminology, distinguishing features, formation conditions, information derived from Pliny’s books, past and current supply areas and, finally, archaeometric provenance issues are addressed for each type of material. As for chalcedony, a comprehensive note on moganite has been included. The next section focuses on chert, flint and jasper. Given the large amount of materials available on this topic, the present review must necessarily be considered introductory and partial. The discussion aims to provide useful indications on how to distinguish chert from flint and chert from jasper; secondly, the information provided by Pliny and the archaeometric state of the art on these materials is reviewed. The last section examines quartz varieties: hyaline quartz (rock crystal), milky quartz, smoky quartz, rose and pink quartz, amethyst, citrine, prasiolite and blue quartz. An exhaustive mineralogical discussion on quartz is beyond the scope of this review; conversely a review of the historical information is provided, together with a brief list of major supply areas, a summary of the archaeometric studies performed on these materials, as well as an indication of the geological literature which can be used proficiently for provenance studies.