The novel molecularly imprinted microspheres for four phenylarsonic compounds have been firstly prepared with the reversible addition-fragmentation chain transfer polymerization in a suspension system. The resulting polymeric microspheres were characterized by infrared spectrum, scanning electron microscope and differential scanning calorimetry. With serial adsorption experiments, the polymeric microspheres showed highly specific molecular recognition, fast mass transfer rate and robust adsorption of the substrates. Then, the imprinted polymer was used as the solid-phase extraction adsorbent to extract the phenylarsonic compounds from the feeds, edible chicken and pork. The cartridge was washed with 2 mL ethyl acetate and eluted with 3 mL of methanol- acetic acid (90:10, v/v). The recoveries of the molecularly imprinted solid-phase extraction (MISPE) column ranged from 83.4% to 95.1%. This work provided a versatile approach for the specific extraction of the organoarsenic compounds from complicated matrices and exhibited a bright future for the application of MISPE column.