AbstractOn‐site Raman analyses were performed at the Musée national de Céramique, Sèvres, France, on select rare items of the earliest known European hard‐paste porcelains and stonewares, produced from ca 1710 to 1750 in the Meissen workshop (Saxony) founded by J. F. Böttger and E. W. von Tschirnhaus. Characteristic on‐site Raman signatures have been obtained for white Sake bottles from ca 1715, a green bowl depicting a purple landscape dated 27th August 1726 and a figurine and coffee cups produced in the middle of the eighteenth century. In addition, some artefacts (a red polished stoneware cup from ca 1710 to 1715, a white ewer stopper from ca 1725, a blue underglaze decorated flat stopper believed to have been manufactured after 1719 and decorated coffee cups) were analysed at the laboratory. Raman spectra identified different types of mullite‐rich bodies, including calcium‐rich and quartz‐containing pastes. Different types of glazes and pigments (haematite, Naples yellow, cassiterite, lapis lazuli, etc.) have also been identified. The results are discussed in the light of previous chemical analyses and historical records. We propose characteristic parameters to discriminate between the different production technologies. Copyright © 2006 John Wiley & Sons, Ltd.