Ferroelectrics are considered next generation photovoltaic (PV) materials. In this work, a switchable and large PV effect is demonstrated in a Pb-free ferroelectric 0.5Ba(Zr 0.2 Ti 0.8 )O 3 -0.5(Ba 0.7 Ca 0.3 )TiO 3 (BZT-BCT) thin film fabricated by a pulsed laser deposition technique. The material shows a remarkable PV output of 0.81 V due to its morphotropic phase boundary composition. The observed PV effect is analyzed on the basis of the interfacial Schottky barrier and bulk depolarization field. The poling dependent PV studies revealed that although the Schottky and depolarization field contribute to the PV effect, the latter dominates the PV response beyond the coercive field. Additionally, the importance of this compound in the field of a self-biased photodetector is elucidated in terms of calculated photodetector parameters such as responsivity and detectivity. The explored results will bring significant advancement in the field of ferroelectric PV, UV solid state detector applications and also give an additional dimension to the multifunctional ability of the BZT-BCT system. © 2019 Author(s).