Two tetradentate Pt(II) complexes with peripheral bulky-group hindrances [Pt(pzpyOczpy-B1) and Pt(pzpyOczpy-B2)] were synthesized and fully investigated for their structural and blue phosphorescent properties. Both X-ray crystallography and computational simulation revealed that bulky substituents incorporated into the C-pyrazolyl and C-pyridinyl positions lie out of the cyclometallated plane, thus alleviating the intramolecular distortions as well as reducing the intermolecular interaction in the solid state. In dichloromethane, their emission peaks at 460 nm with a narrow full width at half-maximum (FWHM) of less than 50 nm, and the photoluminescent quantum yields are over 95% with short decay lifetimes (<5 μs). Solution-processed blue devices are fabricated based on the two complexes. Device A based on Pt(pzpyOczpy-B1) shows excellent electroluminescent performances with the maximum current efficiency, power efficiency, and external quantum efficiency of 47.0 cd/A, 24.6 lm/W, and 22.9%, respectively. The understanding on inert peripheral hindrances provides an effective approach to designing Pt(II) complexes for high-quality blue phosphorescent emitters.