AbstractRecent excavations at Palù di Livenza (northeastern Italy) revealed a multiphase Neolithic pile dwelling dated between ca. 4,300/4200 and 3,600 cal BC. Three lumps with teeth imprints and a larger amorphous piece from the Late Neolithic layers have been studied by X‐ray computed micro‐tomography (microCT) and synchrotron Fourier‐transform infrared spectroscopy (FTIR). FTIR spectra match well that of birch bark tar and microCT of the larger piece has revealed a rolled‐up structure likely corresponding to bark rolls. The lumps of birch pitch were probably chewed to soften the tar prior to be used as hafting adhesive or therapeutic substance. The rolled‐up inner structure of the larger piece and the remains of birch bark tar and abundant charcoals on its surface suggest it probably corresponds to a rare waste product from allothermic tar production.