Reactions of the alkyl isocyanide fac-[Tc­(CO)3(CNR)2Cl] complexes (2) (CNR = CN n Bu or CN t Bu) with the sterically encumbered isocyanide CNp-FArDarF2 [DArF = 3,5-(CF3)2C6H3] allow a selective exchange of the carbonyl ligands of 2 and the isolation of the mixed-isocyanide complexes mer,trans-[Tc­(CNp-FArDarF2)3(CNR)2Cl] (3). Depending on the steric requirements of the residues R, the remaining chlorido ligand can be replaced by another isocyanide ligand. Cationic complexes such as mer-[Tc­(CNp-FArDarF2)3(CN n Bu)3]+ (4a) or mer,trans-[Tc­(CNp-FArDarF2)3(CN n Bu)2(CN t Bu)]+ (6) have been prepared in this way and isolated as their PF6 – salts. mer,trans-[Tc­(CNp-FArDarF2)3(CN n Bu)2(CN t Bu)]­(PF6) represents to the best of our knowledge the first transition-metal complex with three different isocyanides in its coordination sphere. Since the degree of the ligand exchange seems to be controlled both by the electronic and steric measures of the incoming isocyanides, we undertook similar reactions with the sterically less demanding p-fluorophenyl isocyanide, CNPhpF, which indeed readily led to the hexakis­(isocyanide)­technetium­(I) cation through an exchange of all ligands in the staring materials [Tc2(CO)6(μ-Cl)3]− or fac-[Tc­(CO)3(CNR)2Cl]. The influence of the substituents at the isocyanide ligands in such reactions has been reasoned with the density functional theory-derived electrostatic potential at the accessible surface of the corresponding isocyanide carbon atoms.