We report the iridium-catalysed desilylative acylation of styryl and dienyl silanes by acid anhydrides to afford (E)-alpha,beta-unsaturated ketones. The [{Ir(mu-Cl)(cod)}(2)] catalyst is the first non-rhodium complex successfully applied for this type of transformation. Stoichiometric reaction of [{Ir(mu-Cl)(cod)}(2)] with (E)-trimethyl(4-chlorostyryl)silane was carried out to gain insight into the reaction mechanism. (C) 2016 Elsevier B.V. All rights reserved.