Food safety is the core issue in the field of global public health, which is directly related to human health, social stability, and economic development. The development of reliable, sensitive, and efficient detection technology has far-reaching significance for monitoring harmful substances in food and protecting consumer health. In recent years, combining the excellent adsorption performance of hollow materials and the high selectivity of molecular imprinting technique to targets, hollow molecularly imprinted materials have attracted widespread attention of researchers, which can be used as new adsorption materials for sample pretreatment and construction of detection methods. This article reviews the preparation methods for hollow materials and the synthesis approaches for hollow molecularly imprinted polymers and discusses the application of such new materials in detection of antibiotic residues, pesticide residues, mycotoxins, and other harmful substances in food. It also provides an outlook on future research and development prospect for establishment of food safety detection methods using the hollow imprinted polymers.