This paper presents a new alternative analytical tool for determining the composition of archaeological ceramics - total reflection X-ray fluorescence analysis (TXRF). TXRF is a useful technique for the simultaneous determination of elements with atomic number >12. It is a variant of energy dispersive X-ray fluorescence (EDXRF) for the analysis of small samples placed on a flat carrier and it presents the advantage of minimizing matrix effects. The technique has been compared with clay reference material analysed by neutron activation (NAA) in order to test its sensitivity and accuracy for determining the elemental composition of such material. At the current stage of research the technique can produce precise semi-quantitative results with a simple sample preparation process. The semi-quantitative results show that TXRF can be a suitable technique in the multi-elemental characterization of archaeological ceramics, obtaining data useful for archaeological interpretation, which is illustrated by a case study.