Two kinds of samples of Early and Late Neolithic ceramic sherds of pots from excavations of sites located in Dnepr-Dvina and Low Don region (Serteya II and Rakushechny Yar) were investigated for multi-analytical comparison. The methods include thermogravimetric analysis, X-ray powder diffraction, X-ray photoelectron spectroscopy and method of standard contact porosimetry. The pottery manufactured in Serteya II and Rakushechny Yar has different clay sources, but close mineral composition. Inner sides of sherds are less thermally durable as a result of the contact with cooking meal or boiling water in ancient times: They lose more mass during thermogravimetric measurements. At the same time, the minerals in outer sides of the samples are partly destroyed because of contact with fire in the past. According to differential scanning calorimetry curves, there are thermal effects above 1000 degrees C in all sherds due to mullite formation. There are organic C-F bonds and sharp endothermic peaks at 600-750 degrees C in samples from Serteya II site. In addition to elevated level of nitrogen and phosphorus and carbon black layer on the inner side, it allows to propose that the pot from Serteya II was used for cooking. The sherds from both sites have close overall porosity, but in case of Serteya II size of mesopore is more isotropic.