AbstractControlling exciton dynamics at organic semiconductor interfaces is of fundamental and practical importance, for example, in an organic field‐effect transistor (OFET) photomemory that possesses multifunctional applications. Moreover, the intrinsic properties of embedded charge storage layer may limit the device performances. This report introduces a concept of tunneling‐effect‐assisted interfacial charge trapping and takes full benefit of inherent rich surface traps of dielectrics for OFET photomemory. By controlling the thickness of barrier interlayer between active channel and dielectric, the trapped charge injection and dissipation can be regulated precisely. As a result, excellent transistor characteristics display an inconspicuous threshold voltage shift and hysteresis in dark or light exposure, while the same device can exhibit an outstanding memory behavior upon a gate bias pulse in bright situation. Without any additional materials handling such as photoactive charge storage layer into the construction, it can promise a low‐cost, facile, and versatile device fabrication.