Solar photovoltaics, particularly organic/inorganic halide-based perovskite solar cells (PSCs) with high efficiency and cost-effective solution processing, have shown immense potential in harnessing renewable energy to various cause and sustainable economy in recent decades. Though the power conversion efficiency (PCE) of existing PSCs geared up to 26.7% steadily with some fraction of improved stability to earlier ones, there are still some untraceable challenges regarding the upscaling and stability of these promising perovskite-based solar cells. The present chapter highlights the recent developments in PSCs to their peer fabrication, performance, and commercialization. In addition, the chapter also provides in-depth knowledge of various factors affecting solar cell efficiency with possible remedies such as by using two-dimensional (2D) materials as electrodes, additives, and charge transport layers to overcome them. Therefore, this chapter will be helpful to understand the importance of 2D materials, particularly electrode materials and additives, and the existing charge (electron–hole) transport to enhance the power conversion efficiency of perovskite with relatively improved stability of solar cells from laboratory to commercial applications.