A facile synthesis of highly soluble, axially substituted titanium(IV) phthalocyanines is described. The reaction of tetra-tert-butylphthalocyaninatotitanium oxide tBu4PcTiO with the chelating agents 3a−3i containing oxygen or sulfur as donor atoms leads to the formation of axially substituted tBu4PcTiX (X = functionalized catechols, dithiocatechol, and dihydroxynaphthalene). Following the same procedure a dimeric sandwich-like complex could be also synthesized from the reaction of tBu4PcTiO with tetrahydroxy-p-benzoquinone. All compounds were characterized by IR, UV/Vis, MS, 1H and 13C NMR spectroscopy, and elemental analysis. The axially substituted titanium phthalocyanines show high solubility and a low aggregation tendency due to the steric hindrance arising from the asymmetric peripheral substitution pattern of the macrocycle and the presence of bulky axial ligands. The relevant nonlinear optical (NLO) properties of some of the tBu4PcTiX compounds were determined in order to evaluate the potential role of these new compounds in optical limiting. The correlation between tBu4PcTiX structure and NLO properties is analyzed in terms of the electronic effects of the axial ligand.