A series of azaperylene derivatives such as monoazaperylene (MAPery), 1,6-diazaperylene (1,6-DiAPery), 1,7-diazaperylene (1,7-DiAPery), 1,12-diazaperylene (1,12-DiAPery), triazaperylene (TriAPery), and tetraazaperylene (TetAPery) was synthesized by changing the position and number of nitrogen atoms at the bay region of a perylene skeleton in 1, 6, 7, and 12 positions. The density functional theory (DFT) calculations and electrochemical measurements suggested that the energies of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) states significantly become stabilized with increasing the number of nitrogen atoms, whereas the estimated HOMO-LUMO gaps approximately remain constant. This result is in good agreement with the absorption and fluorescence spectral measurements. Additionally, these steady-state spectroscopic measurements demonstrate the broadened spectra as compared to pristine perylene (Pery). In photophysical measurements, the fluorescence quantum yields (Phi(FL)) significantly decreased as the number of nitrogen atoms increased, whereas much enhanced quantum yields and rate constants of internal conversion (Phi(IC) and k(IC)) were observed. Especially, the increased k(IC) values of TriAPery (k(IC): similar to 10(8) s(-1)) and TetAPery (k(IC): similar to 10(9) s(-1)) are much larger than those of diazaperylene and monoazaperylene derivatives (k(IC): similar to 10(7) s(-1)). These photophysical trends were successfully explained by time-dependent DFT (TD-DFT) calculations. Finally, the characteristic protonated and deprotonated processes of nitrogen atoms in azaperylenes under acidic conditions were monitored utilizing absorption and fluorescence measurements. The binding constants demonstrate that the nitrogen atoms at 1 and 12 positions of a perylene skeleton are essential for the increased values.