Plant polyphenols are plant secondary metabolites with the hydrophilic character. The distinctive characteristics of the phenolic O-H bond, in plant polyphenols, have been implicated in diverse functional roles to play important roles in long-term health protection. The content of plant polyphenols in Xinjiang medicinal herbs is higher due to the influence of climate and environment. The study on plant polyphenols will be benefit to develop traditional medicine with distinguishing feature in Xinjiang. Since similar chemical structure and property, it is hard and paid-cost to obtain a pure compound by isolation and is a challenge in the study of polyphenols chemistry. Molecularly imprinted polymers (MIPs) have the merit of specific selectivity to template, and monolithic column with good permeability can be used at high flow rate for separation. In view of facts above, in this study, ten MIPs monoliths with the imprinting of natural compounds, including punicalagin, will be prepared considering the matrix, polymerization approach and compositions of MIPs. The new MIPs include ZIP-like MIP, metal pivot-based MIPs in ionic liquid, MIPs based on macromolecular crowding, one-monomer MIPs and β-cyclodextrins-based MIPs. The adsorption capacity of the MIPs will be investigated and the imprinting sites are characterized by adsorptive kinetics and thermodynamics. In addition, the effect of polymerization variables on the structure and performance of the resulting MIPs monolith will be studied. Utilizing the MIPs monoliths, new approaches will be developed to selective extraction the components from medicinal herbs in Xinjiang. Moreover, new perspectives toward polyphenols chemistry will be provided.