Ferroelectric photovoltaic is the emerging field in the area of energy harvesting for converting light energy into useful voltage. Among various ferroelectric materials, Bismuth ferrite (BFO) is the most suitable for photovoltaic applications in terms of narrow band gap. BFO is multiferroic material having ferroelectric and antiferromagnetic ordering at room temperature. Multiferroic materials, which exhibit simultaneously ferroelectric, ferromagnetic, and ferroelastic behaviors, provide opportunities for the potential applications in wide field including storage devices, spintronics, and sensors. But the existence of large leakage current weakens its ferroelectric properties and limits its usage in various applications. To overcome this problem, Lead Zirconium Titanate (PZT), good ferroelectric material has been coupled with BFO in the present work. The multilayered PZT/BFO thin film systems with different periodicity have been deposited using pulsed laser deposition (PLD) technique. The structural and ferroelectric properties have been studied and the effect of periodicity on the ferroelectric properties has been analyzed. The top electrode has been patterned on multilayered PZT/BFO thin film system to study its ferroelectric photovoltaic properties. The photovoltaic characteristics were studied using solar simulator and the results are found to be proficient as compared to bare PZT thin film.