Three isomers of Ti-2@C-84 metallofullerenes, Ti-2@C-84 (I,II,III), have been isolated by the so-called multistage high-performance liquid chromatography (HPLC) method and characterized by laser-desorption time-of-flight mass spectrometry (LD-TOF MS), UV-vis-NIR absorption, and electron energy loss spectroscopy (EELS). Both the HPLC elution behaviors and UV-vis-NIR absorption spectra of these isomers are different from those of the other M-2@C-84 type metallofullerenes of groups 2 and 3 and lanthanide metal atoms. The results indicate that the Ti-2@C-84 isomers possess unique electronic structures, which are substantiated by EELS analyses on the valence state of Ti atoms within these metallofullerenes.