The issue of energy scarcity has become more prominent due to the recent scientific and technological advancements. Consequently, there is an urgent need for research on sustainable and renewable resources. Solar energy, in particular, has emerged as a highly promising option because of its pollution-free and environment-friendly characteristics. Among the various solar energy technologies, perovskite solar cells have attracted much attention due to their lower cost and higher photoelectric conversion efficiency (PCE). However, the inherent instability of perovskite materials hinders the commercialization of such devices. The utilization of scanning tunneling microscopy/spectroscopy (STM/STS) can provide valuable insights into the fundamental properties of different perovskite materials at the atomic scale, which is crucial for addressing this challenge. In this review, we present the recent research progress of STM/STS analysis applied to various perovskites for solar cells, including halide perovskites, two-dimensional Ruddlesden-Popper perovskites, and oxide perovskites. This comprehensive overview aims to inspire new ideas and strategies for optimizing solar cells.