On-surface synthesis has gradually become a prevalent approach to constructing two-dimensional functional monolayers on various substrates. In the present work, the synthesis of self-assembled monolayers (SAMs) of benzothiazole derivatives was conducted at the liquid/solid interface for the first time. Two kinds of nanostructures were achieved on the highly oriented pyrolytic graphite (HOPG) surface via the condensation reaction between aromatic aldehyde derivatives and 2-aminothiophenol (ATP). The formation of thiazole-based self-assemblies was revealed by scanning tunneling microscopy (STM) and further confirmed by X-ray photoelectron spectroscopy (XPS). The successful synthesis of the benzothiazole derivatives not only extends the scope of on-surface reactions but also can be applied in designing multifunctional SAMs at the interface.