This paper explores the development of pottery technology in the Trieste Karst region (North-East Italy) from the Neolithic to the Early Bronze Age (EBA). It also seeks to identify cultural links with other areas by examining potentially imported vessels. Archaeometric analyses (X-ray diffraction and optical microscopy) reveal significant differences between Neolithic ceramics (Danilo–Vlaška Group) and the majority of Late Copper Age (LCA)/Early Bronze Age (EBA) pottery (primarily associated with the Ljubljana Culture and a few with the Cetina Culture). Neolithic pottery displays consistent characteristics across all vessel types, including coarse grain, prevalent sparry calcite temper, and the absence of grog. In contrast, most LCA and EBA vessels exhibit distinct features such as very fine-grained paste, no sparry calcite, notable use of grog temper, higher quartz, muscovite, and flint content. Notably, from a technological perspective, the analyzed Cetina vessels bear a strong resemblance to the majority of LCA ceramics. The differences between Neolithic and LCA/EBA vessels clearly suggest the use of new raw materials, recipes, and techniques, likely reflecting changes in cultural and social contexts and potential connections with the core area of the Ljubljana Culture.