Perovskite solar cells (PSCs) are a promising area of research among different new generations of photovoltaic technologies. Their manufacturing costs make them appealing in the PV industry compared to their alternatives. Although PSCs offer high efficiency in thin layers, they are still in the development phase. Hence, optimizing the thickness of each of their layers is a challenging research area. In this paper, we investigate the effect of the thickness of each layer on the photoelectric parameters of n-ZnO/p-CH3NH3PbI3/p-NiOx solar cell through various simulations. Using the Sol–Gel method, PSC structure can be formed in different thicknesses. Our aim is to identify a functional connection between those thicknesses and the optimum open-circuit voltage and short-circuit current. Simulation results show that the maximum efficiency is obtained using a perovskite layer thickness of 200 nm, an electronic transport layer (ETL) thickness of 60 nm, and a hole transport layer (HTL) thickness of 20 nm. Furthermore, the output power, fill factor, open-circuit voltage, and short-circuit current of this structure are 18.9 mW/cm2, 76.94%, 1.188 V, and 20.677 mA/cm2, respectively. The maximum open-circuit voltage achieved by a solar cell with perovskite, ETL and HTL layer thicknesses of (200 nm, 60 nm, and 60 nm) is 1.2 V. On the other hand, solar cells with the following thicknesses, 800 nm, 80 nm, and 40 nm, and 600 nm, 80 nm, and 80 nm, achieved a maximum short-circuit current density of 21.46 mA/cm2 and a fill factor of 83.35%. As a result, the maximum value of each of the photoelectric parameters is found in structures of different thicknesses. These encouraging results are another step further in the design and manufacturing journey of PSCs as a promising alternative to silicon PV.