Reversible supramolecular self-assemblies have attracted increasing attention in nanoscience and technology during the past few years due to their potential application in the extreme miniaturization of switches and other devices. The building blocks concerned can respond structurally, electronically, optically, and mechanically to external stimuli. Herein, we focus on the recent progress of the supramolecular self-assembly reversibly triggered by temperature, light, electric current, metal ions and protons at the solid-liquid interface. Following this general roadmap, supramolecular systems based on H-bonds, azobenzene derivatives, triple-decker complexes, and the guanine motif are successively discussed in this review. Notably, these reversible phase transformations can be probed by the scanning tunneling microscopy (STM) technique, which has been proven as an effective tool in surface science.