Self-assembly provides an effective approach for the fabrication of supramolecular complexes or heterojunction materials, which have unique properties and potential applications in many fields. In this study, the self-assembled structures of stearic acid (SA) and nucleic acid base, guanine (G), are formed at the liquid-solid interface. Two main configurations, namely SA-G-SA and SA-G-G-SA, are observed and the intermolecular recognition mechanism between G and SA is proposed from the hydrogen-bonding point of view.