Regenerated cellulose microspheres (RCM) with controllable sizes and architectures are prepared via electrospraying from environmental-friendly NaOH/Urea aqueous system. The particle size and shape of RCM is mainly dependent on the interplay among the electrical force, surface tension, and viscous force. Particle size can be reduced to a certain extent by increasing voltage and decreasing surface tension, electrode spacing, solution concentration, degree of polymerization, and flow rate. The deformation of droplets, which is peculiarly prone to occur for low viscosity and long electrode spacing, results in elongated spheres, tear-shaped particles, wedge-shaped particles, and banding shaped particles besides micorspheres. The sophericity and uniformity of particles generally become worse as a result of the deformation of droplets. RCM possess good porosity and large specific surface area after regeneration. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40656.