Five cationic iridium(III) complexes with fluorinated cyclometalating tetrazole ligands [Ir(dfptrz)(2)L](+), where Hdfptrz = 5-(2,4-difluorophenyl)-2-methyl-2H-tetrazole and L = 2,2'-bypiridine (1F), 4,4'-ditert-butyl-2,2'-bipyridine (2F), 1,10-phenantroline (3F), 4,4'-bis(dimethylamino)-2,2'-bipyridine (4F), and tert-butyl isocyanide (5F), were prepared following a one-pot synthetic strategy based on a bis-cyclometalated solvato complex obtained via silver(I)-assisted cyclometalation, which was then reacted with the proper ancillary ligand to get the targeted complexes. The X-ray crystal structures of 2F and 4F were determined, showing that the tetrazole ligands are in a trans arrangement with respect to the iridium center. Electrochemical and photophysical properties, along with density functional theory calculations, allowed a full rationalization of the electronic properties of 1F-5F. In acetonitrile solution at 298 K, complexes 1F-3F, equipped with bipyridine and phenanthroline ligands, exhibit strong vibronically structured luminescence bands in the blue region with photoluminescence quantum yields (PLQYs) in the range 56-76%. This behavior is radically different from the nonfluorinated analogues reported previously, which emits in the green region from (MLCT)-M-3 excited states. 4F shows relatively strong emission (PLQY = 40%) of charge transfer character centered on the amino-bipyridine ancillary ligand, whereas the emission of 5F is very weak (PLQY = 0.6%), further blue-shifted and attributed to the lowest ligand-centered (3LC) triplet state of the tetrazolyl cyclometalated moiety. A similar photophysical behavior is observed in PMMA at 298 K, whereas in a 77 K matrix, all of the compounds are strong emitters. This novel fluorinated phenyl-tetrazole cyclometalating ligand provides the corresponding iridium(III) complexes with a combination of excited-state energy and redox potentials that make them very promising as photoredox catalysts.