The development of pure-blue-to-deep-blue-emitting ionic phosphors is an ultimate challenge for full-color displays and white-light sources. Herein we report two series of shortwavelength light-emitting cationic iridium(III) complexes with nonconjugated ancillary and cydometalating ligands, respectively. In the first series, nonconjugated 1-[(diphenylphosphino)methyl]-3-methylimidazolin-2-ylidene-C,C-2' (dppmmi) is used as the ancillary ligand and 2-phenylpyridine (ppy), 2-(2,4- difluorophenyOpyridine (cifppy), and 1-(2,4-difluoropheny1)-1H-pyrazole (dfppz) are used as cyclometalating ligands. In the second one, nonconjugated 2,4-difluorobenzyl-N-pyrazole (dfbpz) is used as the cyclometalating ligand and 3-methy1-1-(2-pyridyl)-benzimidazolin-2-ylidene-C,C-2' (pymbi) as the ancillary ligand. The synthesis and photophysical and electrochemical properties, together with the X-ray crystal structures of these complexes, have been investigated. At room temperature, blue-emitting complexes [Ir(ppy)(2)(dppmmi)]PF6 (1) and [Ir(dfppy)(2)(dppmmi)]PF6 (2; PF6- is hexafluorophosphate) show much larger photoluminescence quantum yields of 24% and 46%, respectively. On the contrary, for complexes [Ir(dfppz)(2)(dpprruni)]PF6 (3) and [Ir(dfbpz)(2)(pymbi)]PF6 (4), deep-blue luminescence is only observed at low temperature (77 K). Density functional theory calculations are used to rationalize the differences in the photophysical behavior observed upon changes of the ligands. It is shown that the electronic transition dipoles of cationic iridium complexes 1 and 2 are mainly confined to cyclometalated ligands ((MLCT)-M-3 and LC (3)pi-pi*) and those of complex 3 are confined to all of the ligands ((MLCT)-M-3, LC (3)pi-pi*, and (LLCT)-L-3) because of the high LUMO energy level of dfppz. The emission of 4 mainly originates from the central iridium(III) ion and cyclometalated ligand to ancillary ligand charge transfer ((MLCT)-M-3 and (LLCT)-L-3), in contrast to commonly designed cationic complexes using carbene-type ancillary ligands, where emission originates from the cyclometalated main ligands. Solution-processed organic light-emitting diodes based on complexes 1 and 2 gave bluegreen (498 nm) and blue (478 nm) electroluminescence with maximum current efficiencies of 3.8 and 3.4 cd A(-1), respectively. The results indicate that introducing nonconjugated ligands into cationic iridium complexes is an effective means of achieving short-wavelength light-emitting phosphors.