Abstract Crystalline crosslinked polyethylene microparticles with size distribution averages ranging from 0.374 to 0.944 μm were prepared from immiscible PS and PE blends in the melt phase for microgel applications. The particles were crosslinked either concurrently while blending using dicumyl peroxide or post blending via electron-beam irradiation. The effects of varying the processing temperature, blend duration, and block copolymer compatibilizer content on the particle morphology were studied and it was found that only a decrease in processing temperatures (increase in continuous-to-dispersed phase viscosity ratio) resulted in finer particles for the range of variables tested. The chemical composition of the isolated particles was determined using infrared and nuclear magnetic resonance spectroscopy while the particle morphology was investigated using electron microscopy image analysis in conjunction with thermogravimetric analysis. It was determined that particles produced with and without the block copolymer contained a small amount of PS even after meticulous extraction with a PS solvent (THF). However, the exact location of PS on the PE particles remains obscure.