One hundred and forty-one glass fragments from medieval Ciudad de Vascos (Toledo, Spain) were analysed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The glasses fall into three types according to the fluxing agents used: mineral natron, soda-rich plant ash, and a combination of soda ash and lead. The natron glasses can be assigned to various established primary production groups of eastern Mediterranean provenance. Different types of plant ash glasses indicate differences in the silica source as well as the plant ash component, reflecting changing supply mechanisms. While the earlier plant ash groups can be related to Islamic glasses from the Near East, both in terms of typology and composition, the chemical signature of the later samples appear to be specific to glass from the Iberian Peninsula. This has important implications for our understanding of the emerging glass industry in Spain and the distribution patterns of glass groups and raw materials. The plant ash that was used for the Vascos glasses is rich in soda with low levels of potash, similar to ash produced in the eastern Mediterranean. It could therefore be possible that Levantine plant ash was imported and used in Islamic period glass workshops in Spain. Unlike central and northern Europe where an independent glass industry based on potassium-rich wood ash developed during the Carolingian period, the prevalence of soda ash and soda ash lead glass on the Iberian Peninsula indicates its commercial and technological interconnection with the Islamic east. Our study thus traces several stages leading to the development of a specifically Spanish primary glassmaking industry.