Abstract Superlubricity, characterized by an ultra‐low coefficient of friction (COF) below 0.01, is crucial for reducing energy losses in mechanical systems but remains challenging at high temperatures. This study designed a high‐temperature‐resistant solid–liquid coupled microcapsule containing perfluoropolyether (PFPE) and molybdenum disulfide (MoS 2 ) encapsulated in silica (SiO 2 ) to develop a self‐lubricating composite material for high‐temperature applications. By embedding these microcapsules into a polytetrafluoroethylene (PTFE) matrix, macroscopic superlubricity (minimum COF = 0.005) is achieved in atmospheric environments up to 200–250 °C. The excellent tribological performance is attributed to the synergistic effects of the stress‐responsive release of trace lubricants, the decreased COF of the PTFE matrix at high temperatures, the low viscosity of PFPE oil reducing internal friction, and the formation of a boundary lubrication film by MoS 2 . This work provided a new strategy for enabling low‐wear operation of polymer materials under extreme thermal conditions and holds significant implications for expanding the application boundaries of superlubricity technology.