As a widely occurring natural product, alkaloids have garnered increasing attention in drug research and development. The efficient, convenient, and environmentally friendly separation and detection of alkaloid compounds from diverse natural products has garnered increasing attention in recent research. Molecular imprinting technology (MIT) is recognized as an effective method for the selective extraction and separation of alkaloids from complex samples due to its capacity for specific recognition. To date, no comprehensive review has been published on the separation and purification of alkaloids using MIT, particularly regarding the sustainability aspects of this technology. In this paper, we review the general preparation methods of molecularly imprinted polymers (MIPs) for alkaloids, including bulk polymerization, precipitation polymerization, magnetic polymerization, and emulsion polymerization. Additionally, we summarize various applications of MIPs for alkaloids, such as different forms of MIP‐based solid phase extraction (MISPE) and MIP‐based sensors for alkaloids detection. Finally, we address some unresolved issues and anticipate future developments in the field.