In this study, we report new thermally activated delayed fluorescence (TADF) emitters, AcPYM (10,10′-(pyrimidine-2,5-diylbis(4,1-phenylene))bis(9,9-dimethyl-9,10-dihydroacridine)) and PxPYM (10,10′-(pyrimidine-2,5-diylbis(4,1-phenylene))bis(10H-phenoxazine)), by employing donor units at the 2,5-positions of the pyrimidine acceptor unit. The donor–acceptor–donor (D–A–D) units combined in the linear molecular structure of AcPYM or PxPYM enhanced the horizontally oriented alignment, and the horizontal transition dipole moments were realized by up to 87% in the host matrix. Organic light-emitting diodes (OLEDs) containing AcPYM and PxPYM emitters realized external quantum efficiencies (η_ext) of 16.8% for blue and green emissions.