Halide perovskite is an emerging material with excellent optoelectronic properties, and also widely used in neuromorphic devices. Recently, halide perovskite has been redefined as exhibiting extraordinary multifunction, e.g., photoferroelectricity. Herein, this work employs a composite material consisting of halide perovskite and organic ferroelectric material to develop a new photoferroelectric synapse, and the photoferroelectricity and some synaptic plasticity are investigated. By the corresponding test analysis, it is demonstrated that photoelectricity and ferroelectricity can reinforce each other in this photoferroelectric composite material. Versatile synaptic behaviors of the nervous system, including paired‐pulse facilitation/paired‐pulse depression, post‐tetanic potentiation /post‐tetanic depression, and spiking‐rate‐dependent plasticity, are successfully simulated. Particularly, the classical conditioning in Pavlov's dog experiment can be replicated in the photoferroelectric synapse to realize the learning function of the brain, including memory loss and recovery. This work could be conducive to the application of multifunctional perovskite materials in synapse devices and neuromorphic computing.