Extracting water from air offers a promising route to address the global challenge of water scarcity. However, bionic engineering surfaces for water harvesting often struggle with efficiently coordinating droplet nucleation and desorption. The recently emerging triboelectric effect at the liquid–solid interface offers a novel approach for developing bionic fog harvesting surfaces. In this study, inspired by Namib Desert beetles and lotus leaves, a biomimetic superhydrophobic surface with nanoscale hydrophilic domains is prepared via interfacial self-assembly, exhibiting heterogeneous wettability for effective water harvesting. The essence of interfacial self-assembly lies in the synergy of non-covalent interaction forces, driving the self-assembly of nanoparticles into surface micro-nano hierarchical structures, thereby regulating wettability and increasing potential nucleation sites. Additionally, the triboelectric effect can directly utilize the triboelectric charges to facilitate droplet migration. The triboelectric effect can be generated by flexible mechanical input induced by walking, which enhances interfacial mass transfer, thereby rapidly improving droplet removal and achieving a 39.02% increase in water harvesting efficiency. This study has opened up a new breakthrough for the design of portable and efficient water harvesting systems.