The reaction of cis-[ReO2I(PPh3)2] with tert-butyl isocyanide in benzene led to the isolation of the complex [ReI3(CN-t-Bu)3(PPh3)] (1). The complex is unusual since it contains bulky ligands with large cone angles, i.e. three iodides, three isocyanides with tert-butyl groups and a triphenylphosphine as ligands in a seven-coordinate geometry around the rhenium(III) metal ion.