We investigate the bonding of Si and C-60 both theoretically (by ab initio calculations within the local density approximation to the density functional theory) and experimentally. Starting from the laser ablation of Si and C-60 followed by a supersonic expansion, we first show that it is possible to obtain small stable (C-60)(n)Si-m clusters (with n approximate to m). We then investigate the configuration of the clusters by means of extended X-ray absorption fine structure (EXAFS) measurements and show that Si binds to the pentagonal face of the fullerenes. According to our calculations, such a structure is predicted to be metastable. The calculated bond energy is higher than that of the typical van der Waals bond. It highlights the potential of the Si-C-60 bond to synthesize nanostructured C-60-based materials with high binding energy. (C) 2003 Elsevier B.V. All rights reserved.