This paper provides a detailed technological characterization of the Roman opus sectile glasses (second century AD) coming from the renowned Gorga collection. Nine glass samples corresponding to imitations of the porfido verde antico, cipollino rosso, rosso antico, giallo antico, diaspro nero e giallo, semesanto and agate/alabaster stones were studied. The aim of this study was twofold: (i) archaeometric, i.e., to provide valuable data on the production, raw materials and techniques of these refined Roman glasses that mimic precious stones and (ii) methodological, i.e., to highlight the good performance of combining polished thin sections and local probe measurements for the study of glassy microstructures. Based on the nature of the flux used, the glasses from the samples were classified as either natron-type or mixed-type (natron/plant ash). The latter stem from remelted glasses and contain relict grains of wollastonite that were not found in the pure natron samples. Relict wollastonite crystals appear to be a proficient petrographic marker to spot recycled glasses along with the commonly used chemical fingerprints. Different production and colouring techniques were identified, even for a given type of imitated stone. Metallic Cu, Ca antimonates and Pb-Fe antimonates were the three opacifiers used for the opaque glasses. Based on the crystal morphologies, metallic Cu and Ca antimoniates were possibly synthesized in situ simultaneously with the glass, whilst the Pb-Fe antimonates were prepared ex situ. The working temperatures for these glasses were estimated within the 900–1100 °C range based on the presence and known thermal stability of some identified crystal phases.