Polar surfaces are intrinsically unstable and thus highly reactive due to the uncompensated surface charges. The charge compensation is accompanied by various surface reconstructions, establishing novel functionality for their applications. The present in situ atomic‐scale electron microscopy study directly shows that the atomic step and step‐assisted reconstruction play central roles in the charge compensation of polar oxide surfaces. The flat (LaO)+‐terminated LaAlO3 (001) polar surface, when annealed at high temperature in vacuum, transits to the (015) vicinal surface via the dynamic motion and interaction of atomic steps. While the (015) vicinal surface possesses zero polarization along the surface normal, a thermodynamic ground state is achieved when the in‐plane polarization is fully compensated via the reconstruction of step‐edge atoms; the step‐edge La atoms are displaced from their ordinary atomic sites toward the adjacent Al step‐edge sites, resulting in the formation of negatively charged La vacancies at the corresponding step edges. As confirmed by first‐principles calculations, the observed step reconstruction of (015) vicinal surface can completely cancel both out‐of‐plane and in‐plane electric fields. This hitherto unknown mechanism reveals the central role of step reconstruction in stabilizing a polar surface, providing valuable insights for understanding the novel charge compensation mechanism accompanied by the step reconstruction.