Mineralogical and geochemical results derived from analyses of the pottery ensemble documented in the Cave of Los Gitanos (Castro Urdiales, Spain) are presented in this paper. This site contains an archaeological deposit formed in the mid-fifth millennium cal bc, which has yielded one of the oldest pottery assemblages in northern Spain. The analysis of the pottery remains has focused on both petrographic (thin-section and XRD) and geochemical characterization (SEM–EDS) of samples selected after a macroscopic study. The mineralogical analysis has revealed procurement of raw materials from different sources, as well as different manufacturing processes. In addition, the petrographic analysis has shown different methods of manufacture, such as pottery tempered with calcite, limestone, ophite (ophitic dolerite) and grog, and fabrics with non-modified clays. Variations observed between the oldest assemblage (Sub-levels A4 and A3) and the most recent one (Sub-level A2) suggest a modification in pottery-making practices between the fifth and the third millennia cal bc.