In order to determine the influence of the inorganic support on the asymmetric induction, different chiral chromium(III)-salen complexes have been incorporated within the cavities of zeolites Y, EMT and into the interlamellar region of K-10 montmorillonite. These heterogeneous catalysts are able to promote the asymmetric ring opening of epoxides with trimethylsilylazide to afford chiral azido trimethylsilyl ethers and azido alcohols with modest enantiomeric excess that varies depending on the inorganic support. The factors that have been found to play a negative influence diminishing the enantioselectivity of the supported Cr(III)-salen catalyst compared to the unsupported complexes are the following: (i) the presence of adventitious acid sites, (ii) the encapsulation of no sufficiently stereogenic ligands and (iii) the change in the reaction mechanism from bimetallic to a single metal reaction mechanism.