In summary, the construction of CMASEI plays a crucial role in improving the application of silicon anode materials. After reasonable molecularly modified coatings of ASEI, the kinetics of lithium-ion transport on the surface of silicon-based anode materials showed significant improvement. This not only effectively increased the initial Coulombic efficiency and reduced the consumption of active lithium, but also ensured the structural stability of the silicon-based anode. These molecular strategies can directionally introduce effective components of the SEI, guiding the directional transport of ions and shortening the transport distance, thereby ensuring the stable electrochemical performance of silicon-based anodes. Consequently, this has become one of the crucial technologies in the research of silicon anode. However, there are also some problems in constructing CMASEI of silicon-based anode in this way. First, the design must enable the generation of components within the SEI, which limits the use of materials with high ionic conductivity. Furthermore, to prevent the oxidation of products during subsequent lithiation, stringent reaction conditions are required. Therefore, we put forward several prospects. Developing high ionic conductivity, non-lithium ion-based nano-protective layers could be an intriguing approach for constructing CMASEI. Additionally, CMASEI for aqueous silicon-based anode deserves greater attention.