Herein, we report the synthesis of two novel ionic Ti complexes possessing three [N,O]-type bidentate ligands from the reaction of Fe metallascorpionate ligands possessing extended alcohol groups and TiCl4. The reaction of substituted hydroxyphenyl tetrazole and Fe(ClO4)3 in a molar ratio of 3:1 afforded iron scorpionate metalloligands possessing extended arms, which were characterized by IR spectroscopy and ESI-TOF-MS spectrometry. Their molecular structures were also confirmed as neutral Fe-centered scorpionate complexes by X-ray crystallography, in which the extended alcohol groups adopted a tripodal geometry. Moreover, two different crystals of iron scorpionate metalloligand grown from CH2Cl2 and CH3OH were studied, revealing that, in the latter crystal, the tripod arms are folded and aligned toward the C3-rotational axis of the molecule, whereas the tripod arms are unfolded and spread outward from the rotational axis in the former crystal. These metalloligands are solvatochromatic; a bathochromic shift was observed as the solvent polarity increased. From the reaction, the aforesaid Fe complexes were further reacted with TiCl4 in a molar ratio of 1:1 to produce ionic [TiL3]+[FeCl4]- (L = substituted hydroxyphenyl tetrazole) complexes from the transmetalation of Ti and Fe. The complexes were characterized by various analytical methods including UV/vis and IR spectroscopies, electrospray time-of-flight mass spectrometry (ESI-TOF-MS), and X-ray crystallography.