1,3,5-tribenzylhexahydro-1,3,5-triazine-CrCl3 (TAC-CrCl3) was supported on monodisperse Stober silica and on commercial silica particles. The monolayers of these catalyst particles were successfully prepared with Langmuir-Blodgett technique. The effect of TAC-CrCl3 molecules on the ordering and film-forming of the silica particles was investigated. The particles arrange in domains of hexagonal ordering. but the ordering of particles in the monolayer decreases with increasing Cr loading. These hybrid rnonolayers are active polymerization catalysts. After polymerization. a relatively rough layer of polyethylene molecules covers the catalyst monolayer and this layer is hydrophobic. The monolayers and the polymers coating films were characterized by IR, UV-vis-NIR, and SEM. The method provides a way to fabricate polyethylene films on silica monolavers. (c) 2006 Elsevier Inc. All rights reserved.