Blue phosphorescent platinum complexes with phenylene-bridged pincer ligands, [Pt(dmib)Cl] [1; dmib = m-bis(methylimidazolyl)benzene], [Pt(mizb)Cl] [2; mizb = bis(N-methylimidazolium)benzene], and [Pt(dpzb)Cl] [3; dpzb = m-bis(3,5-dimethylpyrazolyl)benzene], have been investigated theoretically to rationalize the marked differences of their phosphorescence efficiencies. On the basis of density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations, the geometrical and electronic structures, absorption and emission properties, and radiative and nonradiative processes are analyzed in detail. The emission from the emissive lowest triplet state (T-1) originates from a mixture of metal-to-ligand charge-transfer ((MLCT)-M-3) and intraligand charge-transfer ((ILCT)-I-3) states. The calculated radiative decay rate constants of T-1 of the complexes are comparable and in the same order of magnitude with the experimental measurements. Therefore, the potential energy profiles for the deactivation processes from T-1 via temperature-independent and -dependent pathways are explored to reveal the effect of nonradiative decay on phosphorescence. The calculated results indicate that the very weak emission of 3 could be ascribed to the deactivation process via the metal-centered ((MC)-M-3) state, which can be readily accessible via a spontaneous process from the T-1 state. This work provides more in-depth insight into the nature of the emissive excited state, shielding light on a better understanding of the excited-state behavior of phosphorescent platinum complexes.