Ferroelectric materials have been a focus of much research over the last few decades for their unique piezoelectric and optoelectronic properties. Conventional solar cells have been devised based on the photovoltaic effect of semiconductor p–n junctions, with their photogenerated voltage being influenced by the bandgap of the semiconductors, limiting their further development. Ferroelectric photovoltaics have attracted attention for their unusual photovoltaic effect and controllability. The photogenerated voltage that is independent of bandgap along the polarization direction can be generated in ferroelectric materials, undoubtedly making up for the lack of solar cells. Ferroelectric materials have been used in a wide range of piezoelectric, storage, sensor, and optoelectronic because of their unique optical and electrical properties. However, the small photogenerated current of ferroelectric photovoltaic devices is one of the challenges that need to be overcome. Researchers have shown that the photogenerated current of ferroelectric photovoltaic devices can be significantly improved by cation doping and heterostructure construction, reigniting the enthusiasm for the investigation of ferroelectric photovoltaics. This paper reviews a variety of ferroelectric photovoltaic materials, the mechanism of ferroelectric photovoltaics, approaches for improving ferroelectric photovoltaic performance, and the applications and future prospects for ferroelectric materials. New photovoltaic materials and devices have been a research hotspot for recent years. Ferroelectric materials with multiple effects have great potential for applications in the fields of photoelectric detection, photoelectric storage, etc. This manuscript summarizes briefly the mechanism, performance improvement and applications of ferroelectric photovoltaic materials and devices.