Designing solid-state perovskite oxide solar cells with large short circuit current (JSC) and open circuit voltage (VOC) has been a challenging problem. Epitaxial BiFeO3 (BFO) films are known to exhibit large VOC (>50 V). However, they exhibit low JSC (≪μA/cm2) under 1 Sun illumination. In this work, taking polycrystalline BiFeO3 thin films, we demonstrate that oxygen vacancies (VO) present within the lattice and at grain boundary (GB) can explicitly be controlled to achieve high JSC and VOC simultaneously. While aliovalent substitution (Ca2+ at Bi3+ site) is used to control the lattice VO, Ca and Ti cosubstitution is used to bring out only GB-VO. Fluorine-doped tin oxide (FTO)/Bi1-xCaxFe1-yTiyO3-δ/Au devices are tested for photovoltaic characteristics. Introducing VO increases the photocurrent by four orders (JSC ∼3 mA/cm2). On the contrary, VOC is found to be <0.5 V, as against 0.5-3 V observed for the pristine BiFeO3. Ca and Ti cosubstitution facilitate the formation of smaller crystallites, which in turn increase the GB area and thereby the GB-VO. This creates defect bands occupying the bulk band gap, as inferred from the diffused reflection spectra and band structure calculations, leading to a three-order increase in JSC. The cosubstitution, following a charge compensation mechanism, decreases the lattice VO concentration significantly to retain the ferroelectric nature with enhanced polarization. It helps to achieve VOC (3-8 V) much larger than that of BiFeO3 (0.5-3 V). It is noteworthy that as Ca substitution maintains moderate crystallite size, the lattice VO concentration dominates GB-VO concentration. Notwithstanding, both lattice and GB-VO contribute to the increase in JSC; the former weakens ferroelectricity, and as a consequence, undesirably, VOC is lowered well below 0.5 V. Using optimum JSC and VOC, we demonstrate that the efficiency ∼0.22% can be achieved in solid-state BFO solar cells under AM 1.5 one Sun illumination. Copyright © 2020 American Chemical Society.