A pioneering integration of oxide semiconductor memristors with optoelectronic features is presented, surpassing binary limitations to realize multi‐valued synaptic operations. Through Pt/Ga2O3/Pt memristors, their structural and electronic attributes via atomic force microscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy are explored. Demonstrating unipolar resistance switching with remarkable endurance and retention, the devices exhibit intricate light‐resistance correlations, yielding substantial photoelectric effects in distinct resistance states. Investigating synaptic behaviors, potentiation, and depression akin to biological synapses are unveiled, facilitating learning and memory processes. The standout achievement lies in attaining quaternary memory storage within a single device. Empirical data and simulations validate this concept, showcasing the potential for encoding and sustaining multiple memory states. This innovation heralds transformative possibilities, emphasizing oxide semiconductor memristors as a gateway to quaternary memory storage and enhanced synaptic functions. In essence, this work pioneers optoelectronic synaptic devices with expanded memory capabilities.