Here, pyridopyrazino[2,3-b]indole based D–A assembly was designed and synthesized with modulation of various electron-donating/withdrawing substituent and characterized by various spectroscopic methods. Pyridopyrazino[2,3-b]indole derivatives show inbuilt intramolecular charge transfer (ICT) transitionwhich established D–A building in molecules and induces blue-green emission in the solution state. However, solid-state emission characteristics explore the emission property of some molecules towards aggregationinducedemission (AIE) effect which leads to the formation of emissive nano aggregates in THF/H₂O mixture. Alteration of substituent on pyridopyrazino[2,3-b]indole segment effectively tune electrochemical property and resulting LUMO energy level was found to be comparable with reported electron transporting/ntypematerials. These properties and good thermal stability indicate that molecules have the potential to be used as solid-state emitter and n-type materials in optoelectronic devices.