Narrow- or monodisperse poly(divinylbenzene-co-acrylonitrile) (poly(DVB-co-AN)) microspheres with reactive cyano group were prepared by distillation-precipitation polymerization of divinylbenzene (DVB) and acrylonitrile (AN) in neat acetonitrile with 2,2'-azobis(isobutyronitrile) (AIBN) as initiator in the absence of any stabilizer or additive without stirring. The effects of the comonomer feed on the morphology and the size of poly(DVB-co-AN) microspheres were investigated. All the polymer microspheres were characterized with scanning electron microscopy and FT-IR spectra.