Unique black coatings were observed in the inner wall of pottery shreds excavated from Keeladi, Tamilnadu, India. Raman spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy were used to understand the nature of the coating. The analysis revealed the presence of single, multi-walled carbon nanotubes and layered sheets in the coating. The average diameter of single-walled carbon nanotube found to be about 0.6 ± 0.05 nm. This is the lowest among the single-walled carbon nanotubes reported from artefacts so far and close to the theoretically predicted value (0.4 nm). These nanomaterials were coated in the pottery's that date backs to sixth century BC, and still retain its stability and adhesion. The findings of nano materials in the pre-historic artifacts, its significance and impact are discussed in this article.