The hardware‐level construction of artificial synapses, mimicking the functionality of biological synapses, is widely acknowledged as a pivotal stride in artificial intelligence systems. Particularly, establishing all‐optical artificial synapses for neuromorphic computing, leveraging on‐chip optical interconnects instead of conventional wired connections, has garnered widespread attention. Here, high‐quality CsPbBr3 single crystals are synthesized, and intriguing relaxation processes associated with reversible photo‐induced phase transition (PIPT) are observed, leading to a corresponding change in the birefringence effect. The birefringence change is systematically analyzed by an optical system. The relaxation time of reversible PIPT is similar to the behavior patterns of biological synapses, enabling the device to mimic synaptic features. The device successfully mimics excitatory/inhibitory synaptic behaviors such as EPSP/IPSP, PPF, SDDP, SFDP, and SIDP by using 1310 nm signal. Furthermore, the device continues to exhibit excitatory/inhibitory synaptic functionality when 940 and 1550 nm signals are applied, achieving multi‐wavelength synaptic behaviors. The all‐optical devices have the advantages of low crosstalk, fast signaling, and wide optical bandwidth, which lays the foundation of all‐optical hardware for neuromorphic computing systems.