Ethylbisindenyl zirconium dichloride (Et(Ind)2ZrCl2) and the MAO methylalumoxane (MAO) co‐catalyst were heterogenized on Davision silica 955 partially dehydroxylated at 275 °C, following the concept of equilibrium adsorption. The influence of MAO on the electronic environment resulting from the heterogenization was investigated using XPS. Heterogenization of Et(Ind)2ZrCl2 and MAO on the above silica generated two types of zirconocenium cations (Cation 1 and Cation 2), independent of the heterogenization methods. Based on the postulated surface chemistry, Cation 1 is presumed to be in the form of an ion‐pair [SiO]−[Et(Ind)2ZrCl]+, whereas Cation 2 is presumed to be a trapped multi‐coordinated crown complex of MAO. In the absence of MAO, only Cation 1 is formed. The present study provides some support for the postulated surface chemistry regarding heterogenization of Et(Ind)2ZrCl2 and MAO on silica. Copyright © 1999 John Wiley & Sons, Ltd.