The structure of small organic molecules with self-assembly characteristics is generally composed of three parts: one end of the molecule is the anchor group, the other end is the tail group that regulates the performance, and the middle is connected by a backbone. Such molecules usually use silanes, thiols, acids, etc. as anchor groups; The tail group is generally composed of an electron-withdrawing group or an electron-donor group; The backbone is generally composed of alkyl or aromatic chains of different lengths. This article presents an overview of the attributes and properties exhibited by these self-assembling molecular architectures over the past decade and summarizes their applications in optoelectronics, biomedical science, sensing, and corrosion prevention domains. By comparing the advantages and disadvantages of such molecular self-assembly film-forming modified devices, the structure-activity relationship is summarized, and some assumptions are put forward for such molecules in combination with the research of our group.