Abstract This investigation focuses in detail on the analysis of discoveries in South Moravia – important sites from the Roman period in Pasohlavky and Musov. Using X-ray fluorescence analysis and micro-analysis we help identify the techniques of enamel paint and give a thorough chemical analysis in details which would not be possible to determine by means of macroscopic examination. We thus address the influence of elemental composition on the final colour of the enamel paint and describe the less known technique of combining enamel with millefiori. The material analyses of the metal artefacts decorated with enamel paint significantly contribute to our knowledge of the technology being used during the Roman period.