A photoelectronic switch of a multilevel memory device has been achieved using a meta-conjugated donor-bridge-acceptor (DBA) molecule. Such a DBA optoelectronic molecule responds to both the optical and electrical stimuli. The device exhibits good electrical bistable switching behaviors under dark, with a large ON/OFF ratio more than 106. In cooperation with the UV light, photoelectronic ternary states are addressable in a bistable switching system. On the basis of the CV measurement, charge carriers transport modeling, quantum chemical calculation, and absorption spectra analysis, the mechanism of the DBA memory is suggested to be attributed to the substep charge transfer transition process. The capability of tailoring photoelectrical properties is a very promising strategy to explore the multilevel storage, and it will give a new opportunity for designing multifunctional devices.