Pt(II) complexes are promising phosphorescent materials for organic light-emitting diode (OLED) applications in the fields of display, lighting, healthcare, aerospace, and so on. A series of novel biphenyl ()-based tetradentate 6/5/6 Pt(II) emitters using oxygen or carbon as a linking atom was designed and developed. The intermolecular interactions in crystal packing, electrochemical, and photophysical properties of the -based Pt(II) emitters and also their excited-state properties were systematically studied, which could be effectively regulated by ligand modification through linking group control; however, their emission spectra nearly showed no change. All the -based Pt(II) emitters exhibited vibronically featured emission spectra with dominant peaks at 502-505 nm and photoluminescent quantum yields of 24-34% in dichloromethane solution. Green OLED using as an emitter achieved a maximum brightness () of 16,644 cd/m.