Hydrotalcite (HT) nanolayers have been grown directly on carbon fibers by carbonization and subsequent hydration of electrospun PVA/PEO/MgAl-nitrate fibers. The growth of the layered material was ascertained by X-ray diffraction and electron microscopy techniques. High resolution transmission electron microscopy indicated that HTs are adhered on the carbon fibers. The HTs presented very small crystallite sizes, which enhance the accessibility of their basic centers compared to bulk HTs, leading to significant differences in terms of catalytic activity. (C) 2014 Elsevier B.V. All rights reserved.