The composition and structure of a membrane determine its functionality and practical application. We study the supramolecular polymeric membrane prepared by supramolecular emulsion interfacial polymerization (SEIP) on the oil-in-water droplet via the computer simulation method. The factors that may influence its structure and properties are investigated, such as the degree of polymerization and molecular weight distribution (MWD) of products in the polymeric membranes. We find that the SEIP can lead to a higher total degree of polymerization as compared to the supramolecular interfacial polymerization (SIP). However, the average chain length of products in the SEIP is lower than that of the SIP due to its obvious interface curvature. The stoichiometric ratio of reactants in two phases will affect the MWD of the products, which further affects the performance of the membranes in practical applications, such as drug release rate and permeability. Besides, the MWD of the product by SEIP obviously deviates from the Flory distribution as a consequence of the curvature of reaction interface. In addition, we obtain the MWD for the emulsions whose size distribution conforms to the Gaussian distribution so that the MWD may be predicted according to the corresponding emulsion size distribution. This study helps us to better understand the controlling factors that may affect the structure and properties of supramolecular polymeric membranes by SEIP.