Recently the solar energy, an inevitable part of green energy source, has become a mandatory topics in frontier research areas. In this respect, non-centrosymmetric ferroelectric perovskites with open circuit voltage (V OC) higher than the bandgap, gain tremendous importance as next generation photovoltaic materials. Here a non-toxic co-doped Ba1-x (Bi0.5Li0.5) x TiO3 ferroelectric system is designed where the dopants influence the band topology in order to enhance the photovoltaic effect. In particular, at the optimal doping concentration (x opt ~ 0.125) the sample reveals a remarkably high photogenerated field E OC = 320 V/cm (V OC = 16 V), highest ever reported in any bulk polycrystalline non-centrosymmetric systems. The band structure, examined through DFT calculations, suggests that the shift current mechanism is key to explain the large enhancement in photovoltaic effect in this family. © 2018 The Author(s).