Ferroelectric (FE) materials, a subclass of non-centrosymmetric piezoelectric crystals, exhibit spontaneous and switchable polarization responses. These materials are being used to convert one form of energy into another or to preserve a specific form of energy in the system. Among them, the photon-to-electric energy conversion phenomenon by the FE materials has made them an important class of materials in recent days due to their anomalous photovoltaic (PV) effect, which allows them to convert photon energy into electric energy with a power conversion efficiency that exceeds the Shockley–Queisser limit. By combining PV properties with strain, temperature, and polarization, these materials demonstrate fascinating properties like photostriction, flexo-PV effect, photocaloric effect, photothermal effect, and photoferroelectric effect. Therefore, the observed PV effect in the ferroelectric system and its tunable characteristics with the intrinsic and extrinsic parameters make them potential next-generation optoelectronic materials in terms of both fundamental and technological aspects. However, the development of FE optoelectronic devices is hindered due to their lack of absorption capability and bad electrical conductivity. To address these challenges, researchers have been exploring methods such as interface engineering, bandgap tuning, surface charge manipulation, and plasmonics enhancement. In this chapter, the historical development, detailed understanding of the mechanism, recent progress, and future outlooks of the FE–PV effect will be described.