Human skin shows self‐adaptive temperature regulation through both enhanced heat dissipation in high temperature environments and depressed heat dissipation in cold environments. Inspired by such thermal regulation processes, an interfacial material system with self‐adaptive temperature regulation in the solar‐driven interfacial evaporation system, which can exhibit automatic temperature oscillation to enable pyroelectricity generation while producing water vapor, is reported. The bioinspired interface system is designed with the combination of a thermochromism‐based temperature regulator consisting of tungsten‐doped vanadium dioxide nanoparticles and a polymeric pyroelectric thin film of polyvinylidene fluoride. Under the simulated solar illumination with power density of 1.1 kW m−2, the bioinspired interfacial evaporation system achieves a self‐adaptive temperature oscillation with the maximum temperature difference of ≈7 °C and this system can simultaneously generate water vapor as well as electricity with an evaporation efficiency of 71.43% and a maximum output electrical power density of 104 µW m−2, respectively. The study demonstrates a design of thermal management at the interface of solar‐driven evaporation system to exhibit a self‐adaptive temperature oscillation and offers an alternative approach for the multifunctional harvesting of solar energy. Bioinspired temperature regulation at the interface of the interfacial evaporation system is enabled by using thermochromic VO2 nanoparticles as the solar absorption layer, which can modulate the solar thermal process and also the energy distribution within the system. Integrated with a pyroelectric polyvinylidene fluoride film, the system can simultaneously generate water vapor and electricity during the solar‐driven interfacial evaporation process.