The preparation of (octaaryltetraazaporphyrinato)indium(III) chlorides [aryl =: phenyl (5a), p-tert-butylphenyl (6a), p-(trifluoromethyl)phenyl (7a), m-(trifluoromethyl) phenyl (8a)] and their reactions with aryl Grignard reagents XMgBr to give 5b-8b [X = p-(trifluoromethyl)phenyl] and 5c (R = 3,5-difluorophenyl) are described. The characterization of all compounds by UV-vis, FT-IR, and H-1 and C-13 NMR spectroscopy was performed. The hypsochromic shift of all bands in the absorption spectra of complexes 5a-8a is observed in the sequence 6a < 5a < 7a approximate to 8a. This is associated with the increasing electron-withdrawing character of the aryl substituents in the periphery of the tetraazaporphyrin macrocycle. Compounds 8a,b are very good soluble in organic solvents with 8a exhibiting the higher photochemical stability among the various synthesized species. The optical limiting (OL) properties of the complexes have been studied and correlated with the structure of the (tetraazaporphyrinato)indium(III) complexes and the electronic nature of the different substituents. In particular, the OL effect at 532 nm increases on going from the series of compounds 5 to the series 8.