Perovskite solar cells, as a promising next-generation photovoltaic technology for large-scale application, have demonstrated the advantages of high absorption coefficient, tunable bandgap, considerable photoelectric conversion efficiency and low-cost fabrication. However, the photoelectric conversion process within the device is still not understood clearly. One of the major reasons is that it is difficult to directly observe the space potential inside the device and its effect on the photogenerated charge carriers. The direct measurement and analysis of the space potential inside the device and the clarification of the intrinsic relationship between the space potential and the charge carrier micro-process under illumination and different electric field conditions can reveal the photoelectric conversion mechanism in depth, and thus providing the scientific research basis for the further development. Kelvin probe force microscopy (KPFM), a testing technology that is non-contact, can detect the space potential distribution without any damage to the device, demonstrating the great potential to unveil the working mechanism of perovskite solar cells accurately. Such a characterization method can work under vacuum condition. The KPFM combines Kelvin method of measuring contact potential difference with the scan probe microscopy to characterize internal carrier dynamic behavior with high resolution on a nanometer scale. The study of the spatial potential distribution of semiconductor device plays an important role in understanding the working mechanism of new perovskite solar cells. For example, under an open-circuit condition, the intensity and width of the electric field and space charge region can be obtained from the spatial potential distribution, and the bending direction of the energy band can be judged according to the increase or decrease of the potential. While in a short-circuit case, the generation and transport of charge carriers can be obtained. In this review, we mainly introduce the research progress of the space potential distribution and optoelectronic conversion mechanism in perovskite solar cells. The key mechanism of charge carrier generation, separation, transport and recombination are revealed by using KPFM to directly observe the space potential variations caused by light or electric field. We also prospect the issues and challenges in the future research.