We have investigated the use of Rh(PPh3)(3)Cl/ionic liquid (molten salt) as a thermoregulated and recyclable catalytic system for hydrosilylation. It was found that both conversion and selectivity could be influenced by the alkyl chains attached to the pyridinium and imidazolium cations. The Rh(PPh3)(3)Cl/ionic liquid (molten salt) catalyst system combines the advantages of an ionic liquid with convenient product separation, whilst the catalyst system can be reused at least 10 times without noticeable decrease of activity and selectivity. (c) 2007 Elsevier B.V. All rights reserved.