Archaeological excavations between 1984 and 2001 at the early Christian cemetery church in Sion, Sous-le-Scex (Rhône Valley, Switzerland), brought to light more than 400 pieces of coloured window glass dating from the fifth or sixth centuries ad. The aims of this paper are threefold: first, to characterize the shape, colour and chemical composition of the glass; secondly, to understand whether the production of the coloured window panes followed traditional Roman glazing techniques or was of a more innovative nature; and, thirdly, to provide some indications as to the overall design of these early ornamental glass windows. Forty samples of coloured glass have been analysed by wavelength-dispersive X-ray fluorescence. The results of the chemical and the technological studies showed that most of the glass was produced using recycled glass, particularly as a colouring agent. Some of the glass was made of essentially unmodified glass of the Levantine I type. The results taken together seem to confirm that raw glass from this region was widely traded and used between the fourth and seventh centuries ad. The artisans at Sion were apparently still making use of the highly developed techniques of Roman glass production. The colour spectrum, manufacture and design of the windows, however, suggest that they represent early examples of ornamental coloured glass windows.