The recent advance of the aromaticity concept into the all-metal species enlightens us to explore whether there exist all-metal aromatic hydrogen bond. In order to find out the pure pi-H hydrogen bond, works have been performed to eliminate the possible effects induced by the two negative charges of Al-4(2-) and (AlH)-H-... metallic hydrogen bond. Interesting enough, the delocalized pi electron cloud of all-metal aromatic complexes could shield the interaction between aluminium atom and HF and only all-metal aromatic hvdrogen bond is observed in the vertical orientation. Our results reveal a new kind of hydrogen bond. (C) 2005 Elsevier B.V. All rights reserved.