The design and synthesis of metalloid imprinted materials is a challenge due to lack of a feasible functional monomer. A novel cyclic functional monomer (CFM) was used to develop Sb(III)-ion imprinted polymer (CFM-IIP) for efficient and selective removal Sb(III). CFM possesses positively charged imidazolium moiety and specific cyclic size matching with Sb(III). CFM-IIP has a maximum Sb(III) adsorption capacity of 79.1 mg.g(-1), while that of a noncyclic functional monomer imprinted polymer (NCFM-IIP) is only 30.9 mg Sb(III).g(-1). The relative selectivity coefficients of CFM-IIP compared to NCFM-IIP for Sb(III)/Cl-, Sb(III)/NO3-, Sb(III)/PO43-, Sb(III)/SO42-, and Sb(III)/Cr2O72- were 6.6, 78.4, 5.9, 3.0, and 3.2, respectively. Kinetic data fitted well with pseudo-second-order model. The adsorption between Sb(III) and CFM-IIP was identified to be feasible, spontaneous, and endothermic. zeta-Potential, X-ray photoelectron spectroscopic analysis, and density functional theory calculations revealed the mechanism of Sb(III) adsorption on CFM-IIP is as follows: the microdomain confinement effect, derived from the nanoscale imprinted cavities of CFM-IIP, facilitates the hydrolysis of Sb(OH)(3) to SbO45-, which is subsequently sequestered within the imprinted cavities of CFM-IIP due to the strong electrostatic attraction and size matching of CFM-IIP to SbO45-. Therefore, CFM-IIP is very promising adsorbent for the efficient and selective removal of Sb(III) from aqueous solutions.