Heterogeneous zirconocene catalysts were prepared with an unconventional method by grafting mesoporous silica SBA-15 fiber with ZrCl4 in gas or liquid phase and subsequently with lithium salt of cyclopentadiene (Cp) or indene (Ind). In order to obtain a better understanding of the bonding modes of the zirconium and the ligands, the ZrClx/SiO2 and ZrClxL/SiO2 were now for the first time characterized by several techniques, including elemental analysis, FTIR spectroscopy, H-1 MAS NMR and C-13 CP MAS NMR. The results verify the eta(5)-bonding of the ligands to the metal center, which in turn was discovered to be both mono- and bifunctionally bonded to the silica. The catalysts were tested in ethylene polymerization, in which they yielded polyethylene with moderate activities. (c) 2006 Elsevier B.V. All rights reserved.