Chemical modification of phenothiazine‐benzophenone derivatives tunes the emission behavior from triplet states by selecting the geometry of the intramolecular charge transfer (ICT) state. A fundamental principle of planar ICT (PICT) and twisted ICT (TICT) is demonstrated to obtain selectively either room temperature phosphorescence (RTP) or thermally activated delayed fluorescence (TADF), respectively. Time‐resolved spectroscopy and time‐dependent density functional theory (TD‐DFT) investigations on polymorphic single crystals demonstrate the roles of PICT and TICT states in the underlying photophysics. This has resulted in a RTP molecule OPM, where the triplet states contribute with 89 % of the luminescence, and an isomeric TADF molecule OMP, where the triplet states contribute with 95 % of the luminescence. Rapid and efficient utilization of triplet states to generate room temperature phosphorescence (RTP) or highly efficient thermally activated delayed fluorescence (TADF) is achieved by structural modification to give a planar or twisted intramolecular charge transfer (PICT or TICT) geometry, respectively.