Molecular imprinting technique has been increasingly concerned for preparing tailor-made specific recognition materials. In this work, the molecularly imprinted polymers (MIP) microspheres with eccentric hollow structure were prepared by miniemulsion one-step seed swelling polymerization for specific recognition of bisphenol A (BPA), a typical endocrine disrupter. The obtained MIP microspheres were investigated by TEM and SEM, respectively. The images show that the MIP microspheres are of unique eccentric hollow structure with the average diameter of 210 nm. Due to the presence of hollow structure, most of imprinted sites were distributed in the internal and external surfaces of MIP microspheres and the mass transfer resistance of template molecule decreases significantly. The successful building of imprinted sites was validated by a series of adsorption experiments. The experimental results indicate that the MIP microspheres present fast adsorption rate and could reach adsorption equilibrium within 90 min because of low mass transfer resistance resulted from the hollow structure. Additionally, the MIP microspheres also appear considerable binding capacity, binding selectivity (the imprinting factor of 2.06) and renewability. The binding capacity of MIP could remain at a high level after 5 binding-unbinding cycles. Furthermore, the MIP microspheres present excellent water compatibility and could rebind BPA selectively from aqueous medium because of the adoption of hydrophilic functional monomer and aqueous polymerization environment. Due to these unique characteristics, the MIP microspheres show the application prospect in the fields of environmental protection and detection.