Emitters having a negative energy difference between their lowest singlet and triplet excited states are promising candidates for developing next-generation organic light-emitting diodes (OLEDs) because their inverted singlet and triplet (IST) excited states enable exothermic reverse intersystem crossing, which results in a fast rate constant for reverse intersystem crossing and facilitates the efficient harvesting of triplet excitons. This study reports the development of organic emitters comprising 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene as an electron acceptor and 10H-spiro[acridine-9,9′-fluorene] as an electron donor that exhibit IST-excited states. We confirmed the presence of IST excited states in our emitters using photoluminescence spectroscopy, time-correlated single-photon counting, and excited-state density functional theory calculations. In addition, by varying the number of electron donors and the dihedral angles between the electron donor and acceptor, we identified the underlying reasons for the inversion of the singlet and triplet states. Furthermore, we achieved high external quantum efficiencies of up to 30 % by utilizing the IST emitters as emitting layers in OLEDs.