Since the appearance of the first commercial equipments of Total Reflection X-ry Fluorescence (TXRF) in the beginnings of 1989, the use of this technique in some scientific fields has been widely increased. However, its application to the analysis of archaeological ceramics has not been started yet. The most important feature of TXRF is that it combines and optimizes the advantages of more standardized and well-known techniques such as ICP-MS or EDXRF. TXRF is a suitable technique for analysing multi-elemental solid phase samples without any chemical manipulation, providing semi-quantitative determinations. In addition, it can be also a powerful tool for analyzing multi-elemental aqueous phase samples. This paper shows the basis of TXRF and new advances in the compositional analysis of archaeological ceramics. These advances are concerned with quantitative determinations for 24 elements by means of both microwave acid digestion and Fe selective liquid-liquid extraction processes.