AbstractThis report presents the functioning of a molecular memory device with azo-group-functionalized molecular-junctions between metal nanoelectrodes. These junctions are fabricated by a novel electrostatic-assembly process to incorporate azo-group containing polyelectrolyte (AP) between oppositely charged gold nanoparticles (GNP), functioning as nanoelectrodes. The device exhibits a bistable electronic memory effect induced by charge-transfer between AP and GNP, which can be controlled by photo-excitation of the AP. The ON and OFF memory states were found to have a rectification in the range of ∼5000 – 10000. This study will open avenues for development of next-generation molecular systems and devices to produce novel optoelectronic properties.