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• Literature from 1984 to 2020 regarding grisaille is reviewed. • The spatio-temporal study reflects changes in grisailles composition. • The iron oxide is the main colouring agent identified throughout the centuries. • In Germany, Italy and Czech Republic the copper oxide is in higher proportion. • The main substrate glasses identified are sodium-rich and potassium-rich glasses. This work presents the first review on the characterisation of grisaille stained-glass paint, in order to follow the evolution of the production materials and methods throughout time and provenance. From the literature review, 38 scientific studies regarding the grisaille paint were found, dated between 1984 and 2020. In these works, various samples from the 13th to the 20th centuries belonging to 11 different European countries were characterised. In general, iron oxide was the main colouring agent identified throughout the centuries and countries, except in the Central and South-Central European countries where copper oxide was preferably used. Different metal oxides, such as cobalt, chromium and manganese were also identified in modern samples (19th and 20th centuries), used together with iron oxides. The base glasses generally presented a lower ratio PbO:SiO 2 (~0.5 to 1) than the expected from the historical recipes, and the addition of borax is suggested for grisailles from the 17th century onwards. The proportion between the base glass and colouring agents showed ratios between 1 and 1.5, related to well-balanced grisailles. The present overview, critical analysis and comparison of published studies regarding this glass-based paint allow to draw a spatio-temporal map of the grisaille composition evolution, which reflects the changes in composition regarding the country of provenance and century. [ABSTRACT FROM AUTHOR]