Spherical molecularly imprinted polymer particles for bisphenol A (BPA-MIP) were easily prepared by using a Y-junction microfluidic device. The sizes of the obtained BPA-MIP particles were found to be 86 µm with a narrow size distribution. The binding characteristics were investigated by drawing a binding isotherm to estimate the binding constant and by switching the polarity of solvents to examine the feasibility of use as a medium for affinity chromatography. When dichloromethane was used as a solvent, BPA was strongly bound to the spherical BPA-MIP particles based on hydrogen bond formation; after switching the solvent to methanol, BPA was eluted quantitatively due to the weakening of the hydrogen bonding, suggesting that the spherical BPA-MIP particles can be applied to affinity-type solid-phase extraction for BPA. As the present method can provide a diverse range of spherical MIPs without tedious procedures, MIP-based affinity media will be able to be more readily used as pretreatment and/or purification for various fields.