Polymer microspheres and fibers are formed with a versatile new process, precipitation with a compressed fluid antisolvent. By spraying a 1 wt. % polystyrene in toluene solution into CO2 through a 100-μm nozzle, microspheres are formed with diameters from 0.1 to 20 μm as the CO2 density decreases from 0.86 to 0.13 g/cm3. The uniform submicron spheres produced at high CO2 density are due in part to the rapid atomization produced by the large intertial and low interfacial forces. Fibers, with and without microporosity, are obtained at higher polymer concentrations where viscous forces stabilize the jet. The effect of CO2 density and temperature on the size, morphology and porosity of the resulting polymeric materials is explained in terms of the phase behavior, spray characteristics, and the depression in the glass transition temperature.