Thin-film-based photovoltaics offer affordable solar panels (high energy output per unit cost). Various materials have been used for thin-film solar cells, and still, new materials are being tested. In this work, the overall performance of GeSe is enhanced theoretically from a generic solar structure to a configuration that yields a whopping 33.12% efficiency along with an open circuit voltage of 1.04 V by optimizing various active layers using solar cell capacitance simulator SCAPS. The results have been explained most simply, utilizing the physics behind introducing hole transport layers in solar cells. The work also shows how certain contradictions in parameter values in the literature of GeSe can influence the cell’s performance. The result shows why the substrate structure is better than the superstrate structure. Most of the reported results are on superstrate structure, which might have caused poor performance in previously experimentally produced GeSe solar cells.