Donor-σ-acceptor molecules featuring exciplex emission have been extensively researched for developing thermally-activated delayed fluorescence; however, varying the length of alkyl σ-linker to explore the exciplex emission and to develop efficient exciplex emitters has not been fully conducted. Herein, we report donor-σ-acceptor exciplex emitters (1–3) developed with 9,9-dimethyl-10-phenyl-9,10-dihydroacridine donor, 2,4,6-triphenyl-1,3,5-triazine acceptor, and alkyl σ-linkers of different lengths (−CH2− for 1, –CH2CH2− for 2, and –C...