Silylation of aromatic and heteroaromatic oximes with hydrosilanes in the presence of system CsF/18-crown-6/benzene was studied. Silyl ethers were isolated in yields up to 78%. Mechanism of fluoride ion catalyzed silylation of oximes was proposed on the basis of quantum chemical calculations using the semi-empirical AMI method. (C) 2002 Elsevier Science B.V. All rights reserved.