This project is aimed at the investigation of photovoltac(PV) effect of environmentally friendly ferroelectric materials, in particular bismuth based compositions. In view of safety and environmental protection, lead-free ferroelectric materials are more promising for a wide range of applications in the near future. This study focused on 0.94(Bi0.5Na0.5) TiO3-0.06BaTiO3 (BNBT), which has a composition near the morphotropic phase boundary (MPB) and shows superior ferroelectric properties. A-site dopant (Eu) and two B-site dopants (Nb and Fe) were introduced into BNBT ceramics to improve the ferroelectric/piezoelectric properties of BNBT. Moreover, Nb and Fe dopants were found to be able to enhance the photovoltaic properties of BNBT ceramics. First-principle density functional theory (DFT) calculations were also performed to clarify the role of these dopants in modifying electronic band structure of BNBT, and thus the photovoltaic performance. It is concluded Fe dopant has a great potential in improving the PV property of BNBT ceramics by successfully narrowing the bandgap and inducing stronger asymmetry of the crystal structure. In addition, the spark plasma sintering (SPS) technique was also employed to fabricate BNBT ceramics. Enhanced photovoltaic response was obtained in SPS-produced BNBT ceramics due to the grain size effect.