Abstract: Crosslinker is one of the most important factors that dominate the recognition performance of molecularly imprinted polymer (MIP). In this research, MIP was prepared by using bisphenol A (BPA) as the template molecule, α-methacrylate (MAA) as the functional monomer and bisphenol A dimethylacrylate (BPDMA) as the crosslinker, respectively. The resulted MIP was also compared with those obtained by using dimethyl glycol acrylate (EGDMA) and N, N-methylene diacrylamide (BIS) as the crosslinking agents, respectively. The results indicated that the MIP material prepared using BPDMA as the crosslinker gave rise to the best imprinting factor (5.32) and adsorption capacity (5.05 mg/g), which were far superior to those already reported BPA imprinted materials. The imprinting factors of the materials prepared using EGDMA and BIS as the crosslinking agents were 1.41 and 1.45, respectively, and the adsorption capacities were 0.96 mg/g and 2.79 mg/g, respectively. Thus, cross-linker plays an important role in the recognition property of MIP. The resulted MIP was further applied to enrich BPA from milk. The recovery rate was 95.0%—98.9% and the relative standard deviation was 3.5%—4.2%. These results indicated that the prepared imprinted material could be used for the selective enrichment of BPA from complex systems.