AbstractTo date, the improvement of open‐circuit voltage (VOC) offers a breakthrough for the performance of perovskite solar cells (PSCs) toward their theoretical limit. Surface modification through organic ammonium halide salts (e.g., phenethylammonium ions PEA+and phenmethylammonium ions PMA+) is one of the most straightforward strategies to suppress defect density, thereby leading to improvedVOC. However, the mechanism underlying the high voltage remains unclear. Here, polar molecular PMA+is applied at the interface between perovskite and hole transporting layer and a remarkably highVOCof 1.175 V is obtained which corresponds to an increase of over 100 mV in comparison to the control device. It is revealed that the equivalent passivation effect of surface dipole effectively improves the splitting of the hole quasi‐Fermi level. Ultimately the combined effect of defect suppression and surface dipole equivalent passivation effect leads to an overall increase in significantly enhancedVOC. The resulted PSCs device reaches an efficiency of up to 24.10%. Contributions are identified here by the surface polar molecules to the highVOCin PSCs. A fundamental mechanism is suggested by use of polar molecules which enables further high voltage, leading ways to highly efficient perovskite‐based solar cells.