Preparation of anisotropic particles based on seed phase separation involves multiple processes, and asymmetrical structures and surfaces cannot be produced when anisotropic shapes emerge. In conventional one-pot dispersion polymerization (Dis.P) using cross-linker, only spherical particles are prepared due to rapid and high cross-linking. Herein, monodisperse snowman-like particles with core-shell/hollow structures and partially rough surface were synthesized straightforward by a modified one-pot Dis.P, in which ethylene glycol and water (6/4, vol.) were used as medium, and ammonium persulfate (APS) aqueous solution, vinyl acetate (VA) and/or acrylic acid (AA), divinylbenzene (DVB) and styrene (St) were added at 6 h. The cross-linking of growing particles was confined to exterior (forming cross-linked shell), and gel contents were low, leading to phase separation. Asymmetrical morphologies, structures, sizes and surface roughness were flexibly tuned by varying amounts of APS, VA and/or AA, water and DVB, and DVB adding speed. At low APS contents or high DVB amounts, the inhomogeneous cross-linking of head enabled its phase to separate, producing elongated head. With addition of VA and M, phase separations inside head and body were induced, generating hollow structure. Adding DVB very slowly, nonlinear growth of third compartment occurred, forming bowed head. (C) 2015 Elsevier Inc. All rights reserved.