A series of new luminescent cycloplatinated(II) complexes (5a-8a and 5b-8b) with formulas Pt(bt)(N^O) and Pt(bt)(N^P) have been synthesized [bt = phenylbenzothiazole, N^O = (2-(1H-benzimidazole)-phenyl)diphenylphosphine oxide derivatives for 1a-4a and N^P = (2-(1H-benzimidazole)-phenyl)diphenylphosphine derivatives for 1b-4b]. The crystal structures of the complexes show distorted square planar geometries around the platinum centers. There are no obvious π-π and Pt-Pt intermolecular interactions in the crystal lattice due to the presence of sterically bulky ancillary ligands. Consequently, these complexes exhibit structured monomeric emissions in the range of 527-540 nm in CH2Cl2 solution. The photoluminescent quantum yields of Pt(bt)(N^O) (5a-8a) in CH2Cl2 solution at room temperature are higher than those of Pt(bt)(N^P) (5b-8b). The above result is well consistent with the crystal structural characteristics of the complexes. The structured emission with microsecond radiative lifetimes and the result of TD-DFT calculations indicate that the emissions of these complexes are mainly attributed to a mixed 3LC-MLCT state.