Multiple-resonance thermally activated delayed fluorescence (MR-TADF) materials can exhibit narrow-spectrum characteristics owing to the inhibition of rotation within the molecules. However, the excited states of these MR-TADF materials, which influence the spin-orbit couplings (SOCs) and device efficiencies of organic light-emitting diodes (OLEDs), have not been investigated to date. In this study, we synthesized MR-TADF materials tDABNA-TP, tDABNA-DN, and tDABNA-DOB by incorporating characteristic neutral, donor, and acceptor pendants into 2,12-di-tert-butyl-5,9-bis(4-(tert-butyl)phenyl)-5,9-dihydro-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene (tDABNA). To determine the effect of pendant engineering, we investigated the excited states of the MR-TADF materials, including their singlet and triplet excited states, calculated the SOCs for their optimal reverse intersystem crossing pathways, and determined their maximum external quantum efficiencies (EQEmax) in OLEDs. The OLED with the emitter bearing the neutral pendant (tDABNA-TP) exhibited the highest EQEmax of 20.7% among those with the emitters bearing the donor (16.6%) and acceptor (12.4%) pendants, with a narrow emission range of 472-492 nm. Furthermore, the device with the tDABNA-TP emitter exhibited an operating lifetime of 196 h, which was 1.42- and 1.92-fold longer than those of the devices with the tDABNA-DN and tDABNA-DOB emitters, respectively. Our findings will promote research on the pendant engineering of MR-TADF-based OLEDs.