The structures of the Ir(III) and Pt(II) complexes with metallated 2-phenylbenzothiazole (Bt) and chelating 2-(2-hydroxo)phenylbenzothiazole (Hbt) in the crystalline state and in a CDCl3 solution are studied by X-ray diffraction analysis and H-1 NMR spectroscopy. The structures of the complexes are shown to be cis-C,C-[Ir(Bt)(2)(HBt)] (I) and trans-N,N-[Pt(Bt)(HBt)] (II) (CIF files CCDC 996857 (I) and 995845 (II)). Based on the results of absorption and emission electron spectroscopy, the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) determining the character of long-wavelength optical bands and electrochemical processes are assigned to the orbitals predominantly localized on the {Ir(Bt)} fragment for complex I, whereas for complex II the LUMO is localized on {Pt(Bt)} and the HOMO is localized on the {Pt(HBt)} fragment.