This paper presents an overview of developments in oil-based enamel paint technology in the first half of the twentieth century and discusses the selection of ingredients that had a significant impact on the properties of the paints: pigments, extenders, driers, oils and resins. A review of period literature published in French and English is complemented by analysis of historical oil-based Ripolin enamel paint samples produced in France in the years 1910–1950 and a small selection of artists’ paint tubes of the same era from the Art Institute of Chicago’s reference collection. A range of analytical techniques including x-ray fluorescence spectroscopy (XRF), Fourier transform infrared spectroscopy (FTIR), pyrolysis gas chromatography-mass spectrometry with thermally-assisted hydrolysis and methylation (THM-Py-GCMS), scanning electron microscopy coupled with energy dispersive x-ray spectroscopy (SEM-EDX) and thermogravimetric analysis have been used for the characterisation of the paint samples.