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The introduction of agricultural practices fostered the development of specific technologies for the new subsistence practices and the production of new artefacts. Pyrotechnological structures such as ovens are part of the Neolithic equipment and accompanied the spread of agriculture from the Near East across Europe and the Mediterranean Sea. Ovens located within settlements – mainly domed, above-ground structures – have been traditionally linked to cooking and baking. The function is usually deduced from techno-morphological traits, although experimental approaches or ethnoarchaeological observations have often been used. This article aims to demonstrate the effectiveness of the multidisciplinary approach to understand the function of fire structures. An integrated methodology that combines archaeological analysis, archaeometry, and experimental archaeology has been applied to study the underground ovens of the Early Neolithic site of Portonovo (Marche, Italy) dated to the sixth millennium BCE. Samples of hardened sediment of archaeological ovens’ inner surface and selected pottery fragments were analysed through X-ray powder diffraction to estimate the temperature reached. A life-size replica of an underground oven was then created to perform firing experiments, including pottery firing. Samples of the oven’s walls and experimental vessels were analysed with the same method, and the values were compared. Our results indicate that the Portonovo ovens are potentially multifunctional structures, built for about 700 years, always with the same technique exploiting the natural soil’s insulating properties.