Microporous prussian blue analogue Zn-3[Co(CN)(6)](2)center dot xH(2)O microspheres and micropolyhedrons self-assembled by nanoparticles were synthesized under ultrasonic conditions using poly(vinylpyrrolidone) (PVP) as a surfactant. Obvious self-assembly behavior was observed when the microparticles dispersed in alcohol were dropped on a copper grid or a glass substrate without any further treatment. N-2 adsorption properties confirmed the existence of micropores in both Zn-3[Co(CN)(6)](2) microspheres and micropolyhedrons. The concentration of reactants and the molar ratio of the reactant to the PVP as well as ultrasonic conditions have important effects on the shape and size of the product. A possible mechanism is proposed.