In this work, monodisperse polydopamine (PDA) spheres with tunable diameters have been synthesized through a facile and low cost method using a deionized water and alcohol mixed solvent. The PDA spheres possess surface functional groups (–OH, –NH2), exhibiting an extraordinary versatile active nature. It is demonstrated that the PDA spheres could serve as an active template for the convenient synthesis of various nanostructures, e.g., MnO2 hollow spheres or PDA/Fe3O4 and PDA/Ag core/shell nanostructures. No surface modification or special treatment is required for the synthesis of these nanostructures, which makes the fabrication process simple and very convenient. The novel application of PDA/Fe3O4 spheres as fillers in nanocomposites for high-performance capacitors is demonstrated, indicating a promising practicality. The PDA spheres provide a new general platform not only for the facile assembly of nanostructures but also a green synthetic template for practical applications.