Bisphenol A (BPA) imprinted polymer microspheres were prepared by precipitation polymerization and utilized as sorbents for packing common solid-phase extraction columns. In order to find out the influence of solvent on the size and structure of the microspheres, different ratios of toluene to acetonitrile (0/100, 15/85, 25/75, 30/70, v/v) were used as solvents in the precursor and mainly discussed. Particle size, surface area, and pore volume of BPA-imprinted particles increased with the ratios of toluene in the precursor. The selectivity of the BPA-imprinted particles was evaluated toward structure analogs such as diethylstilbestrol and phenol. Microspheres as prepared were then utilized as sorbents for solid-phase extraction of BPA from urine, with recoveries of 94.63 +/- A 2.85%.