<p indent=0mm>Nature has presented multi-scale, multi-level, and multi-functionally assembled systems during evolution, from single-cell to the higher organisms of multi-cell systems. In the course of both physiological and disease processes, cells carry out a series of molecular events at their surface to promote intracellular communication, thus driving cell proliferation, differentiation and migration. A collection of these interacted cells of different types can help to construct a living system with complete functions. Therefore, the development of molecular modification and assembly technologies at cell surface is the key to explore cell interfacial behavior at the molecular level, which may help to understand interfacial molecular events and biochemical reactions. Meanwhile, molecular modification and assembly technologies can greatly promote the advance of many research and application fields, including biosensing, disease diagnosis, translational medicine, and tissue engineering. Therefore, this review will present the latest research progress, so as to systematically describe the use of molecular probes and assembled materials at the cell surface, such as DNA and peptides, and thus give an outlook on their prospects for analytical applications.