The recent renaissances in the field of ferroelectric oxides are owing to various fascinating phenomena exhibited by them, such as electrocaloric (EC), photovoltaic (PV), photostriction, photo-ferroelectric effect, etc. In this regard, exploring the multifunctional characteristics of the ferroelectric materials are essential for the detailed understanding of the dynamics associated with these phenomena. Consequently, to understand the mechanism of above bandgap PV response observed in the ferroelectric systems, a combined experimental and theoretical study is carried out on the BaTiO3 (BTO)-based ferroelectric oxides. The observed anomalous PV response suggests that the origin of the effect is due to the simultaneous effect of ferroelectric polarization and the band topology of the materials near the conduction band minima. Furthermore, the significant change perceived in the photo-induced dielectric and ferroelectric properties illustrates the influence of the ferroelectric order parameter by the light as an external stimulus. Additionally, the enhanced and tunable EC characteristics demonstrated in the present work reveal site-engineered BTO samples' application potential in efficient solid-state cooling devices. Overall, the work provides insight into understanding the fundamental physics behind the intriguing ferroelectric characteristics.