The unique spontaneous polarization property of ferroelectric material makes it to be a special catalyst in photocatalysis. The spontaneous polarization property can induce the formation of built-in electric field, which can improve the separation of photoelectrons and holes to affect photocatalytic performance. The internal electric field induced by spontaneous polarization can be influenced by multiple factors such as the morphology, the concentration of defect, the type of doped heteroatoms, as well as the composition of heterostructures. Besides, the preparation method, pretreating temperature, the strength of prepolarized external electric field of ferroelectric-based photocatalysts as well as the strength of external mechanical force or external magnetic field in photocatalytic reactions can influence the photocatalytic effectivity via influencing spontaneous polarization-induced internal electric field. Thus, it is urgently to unveil the mystery of structure–activity relationships for ferroelectric materials-based photocatalysts, which is usually uncertain. With this in mind, this review was provided for the role of various complex influencing factors on ferroelectric materials-based photocatalysis based on the latest advancement in the fields of new energy development, environmental remediation. In the beginning, the basic structure and properties of ferroelectric material are given. Then, popular synthesis methods of ferroelectric-based photocatalysts are summarized. After that, two main mechanisms of ferroelectric photocatalysis are discussed. The research progress of ferroelectric photocatalysis is then given emphatically according to the classification of photocatalytic reactions. Finally, the problems existing nowadays and the challenges facing in the future on the application of ferroelectric materials-based photocatalysts are outlined in the summary and outlook section.