The state‐of‐art approach to realize the low rolling resistance of green tires is the high addition of SiO2. However, its dispersion capacity and the interface strength with rubber dominant the final properties of green tires. Here, we systematically study amphiphilic polyoxyethylene sorbitan monooleate, oleylamine, sorbitan monooleate, and oleamide to modify SiO2 through simple hydrogen‐bonded self‐assembly in order to replace the traditional silane coupling agent with low modification efficiency, many side reactions and complex reaction process. The results show that the rolling resistance and processing energy loss of the rubber composite prepared by SiO2 modified with polyoxyethylene sorbitan monooleate and oleylamine are significantly reduced, and other physical and mechanical properties (tensile strength, tear strength, and wear resistance) are also significantly improved compared with the silane coupling agent commonly used in green tire tread. Meanwhile, carbon–carbon double bonds belonging to polyoxyethylene sorbitan monooleate and oleylamine can participate in vulcanization of rubber to strongly improve the dispersion ability of SiO2 and the interface interaction between SiO2 and rubber matrix, so as to develop the fuel‐efficient green tire tread with high performance and low rolling resistance.