Delayed fluorescence (DF) emitters with high color purity are of high interest for applications in high-resolution displays. However, the charge transfer required by high emitting efficiency usually conflicts with the expected color purity. In this work, we investigated the S1/S0 conformational relaxation, spin-orbital coupling (SOC), and vibronic coupling of hot-exciton emitters while hybrid local and charge transfer (HLCT) state tuning was achieved by a structural meta-effect. The meta-linkage leads to suppressed S1/S0 conformational relaxation and weakened vibronic coupling, while the unsacrificed emitting efficiency is largely ensured by multiple rISC channels (Tn → Sm) with thermally accessible triplet-singlet energy gap (ΔEST) and effective SOC. We demonstrated that the unique excited-state mechanism provides opportunities to improve the emitting color purity of hot-exciton emitters without sacrificing emitting efficiency by HLCT state tuning with simple chemical structural modification, for which hot-exciton emitters might play a more important role for high-resolution organic light-emitting diode displays.