Electrochromic smart windows can realize intelligent photothermal regulation by applying a low potential, which is of great significance for energy-saving buildings and achieving low carbon emission. However, the dense structure of conventional metal oxide electrochromic materials limits ion transport efficiency, resulting in poor electrochromic properties. Here, we propose a surface crystal reconstruction strategy for cubic NiO through phosphorylation (P-NiO) to build energetic reactive interfaces and enhance the electrochromic performance. Theoretical simulations and experiments reveal that the introduction of PO