A series of blue dyes, 1,7-diaminoperylene bisimides (2a–2c), was synthesized under mild condition in high yields, and was characterized by 1 H NMR, UV–Vis, HRMS spectra, cyclic voltammetry, differential scanning calorimetry, and thermogravimetric analyses. These molecules undergo an excited-state intramolecular electron transfer reaction, resulting in a unique charge transfer emission. Upon excitation, they show smaller dipole moment changes than those of the asymmetric 1-aminoperylene bisimides (4a–4c); the dipole moments of these compounds have been estimated using the Lippert–Mataga equation. Furthermore, they undergo two quasi-reversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Their optical properties in various conditions and complementary density functional theory (DFT) calculations are reported.