Steady-state fluorescence spectra were measured for 1, 8-naphthahlimide-linker-phenothiazine dyads (NIL-PTZ, where L = octamethylenyl ((CH2)(8)) and 3,6,9-trioxaundecyl ((CH2CH2O)(3)C2H4)), NI-C8-PTZ and NI-O-PTZ, as well as the NI derivatives substituted on the nitrogen atom with various linker groups without PTZ as the reference NI molecule in n-hexane. Normal fluorescence peaks were observed at 367-369 nm in all NI molecules together with a broader emission around 470 nm, which is assigned to the excimer emission between the NI in the singlet excited state ((NI)-N-1*) and the NI moiety of another NI molecule ((1)[NI/NI]*). In addition, a broad peak around 600 nm was observed only for NI-L-PTZ, which is assigned to an intramolecular exciplex emission between donor (PTZ) and acceptor (NI) moieties in the excited singlet state, (1)[NI-L-NI] *. The formation of an intramolecular exciplex corresponds to the existence of a conformer with a weak face-to-face interaction between the NI and PTZ moieties in the excited state because of the long and flexible linkers. The excited-state dynamics of the NI molecules in n-hexane were established by means of time-resolved fluorescence spectroscopy.