Highly crosslinked polymer microparticles have been prepared by precipitation polymerization using high monomer loadings (≥25 v/v %) which generally would lead to bulk monoliths. The microparticle format was achieved by the use of non-solvating diluents either alone or in combination with co-solvents. Two distinct morphologies were observed. Monodisperse smooth microspheres were obtained using a thermodynamically good co-solvent whereas segmented irregular particles were formed with poorer co-solvents. It has been found that during polymerization the forming polymer particles were enriched in the co-solvent and this effect was more pronounced when good co-solvents were used. The type of functional monomer, crosslinker and co-solvent, and the non-solvent/co-solvent ratio were identified as influential parameters on the microparticle morphology. With the proposed methodology molecularly imprinted microparticles have been prepared successfully for three different templates, naproxen, diclofenac and toltrazuril using various functional monomers, crosslinkers and polymerization solvent mixtures.