Tris(trimethylsilyl)silane (TTMSS) promoted free radical reaction in benzotrifluoride (BTF) was investigated. Compared to same reaction using environmentally less desirable tri-n-butyltin hydride (TBTH) in benzene, less quantity of BTF than that of benzene can be used because of slower hydrogen atom transfer from TTMSS than that from TBTH toward primary alkyl radicals. Also, electron-transfer reactions promoted by tris(p-bromophenyl)aminium hexachloroantimonate (TBPA) and FeCl(3) were conducted in BTF. Then, TBPA was found to be effective in BTF comparably to that in methylene chloride. In addition, an interesting observation that FeCl(3) promoted reaction was accelerated by the addition of imidazolium salt was made. All the results suggest that BTF is a tolerable solvent for free radical reaction with TTMSS and electron-transfer reactions using TBPA as well as FeCl(3). (C) 2008 Elsevier Ltd. All rights reserved.