A new luminescent ambipolar semiconductor consisting of 1,8-naphthalimide as an electron-accepting moiety and carbazole as an electron-donating moiety has been synthesized and characterized. The synthesized compound as ambipolar semiconductor has been investigated by using density functional theory calculations coupled with the charge-hopping model and the time-of-flight experimental method. The time-of-flight hole and electron drift mobilities in the synthesized material's layer approached about 10−4 cm2 V−1 s−1 at high electric fields. The exciplex complex is stabilized by the intermolecular hydrogen bond and electron donor-acceptor interactions. The energy of interactions between the molecules in the exciplex complex has been estimated to be about −100 kJ mol−1 by DFT. Non-doped emissive layer organic light-emitting diode (OLED) using the synthesized compound as an emitter exhibited an orange color emission with the Commission International de L'Eclairage chromaticity coordinates of (0.47, 0.49).