Structural superlubricity refers to a state with almost vanishing friction and wear between crystalline surfaces in incommensurate configurations. However, thus far, this phenomenon has been observed only at solid-solid interfaces. Here, we constructed an in situ heterojunction between a crystalline boundary tribofilm and a pressure-induced solid-phase 1–dodecanol molecular layer, achieving structural superlubricity in a liquid-solid interface. This novel superlubricity state, termed phase transition structural superlubricity (PTSS), is induced by incommensurate slip at the in situ heterojunction. Atomic force microscopy experiments and molecular dynamics simulations demonstrated that the friction of in situ heterojunction exhibits a periodicity of 180°. Notably, the PTSS arises when the molecular axis of 1–dodecanol is oriented 90° to the direction of friction. These findings provide a novel design strategy for structural superlubricity and bridge the gap between liquid and solid superlubricity, shedding substantial light upon achieving structural superlubricity across a broad range of environments.