A hierarchical silver nanostructure with improved antibacterial property was fabricated utilizing silver coordination polymer. Octadecanethiolate⁻silver polymer was synthesized to have a layered structure and was coated on silicon wafer by drop-casting method utilizing hydrophobic⁻hydrophobic interaction. Thus, the silver coordination polymer was calcined under reductive condition to produce zero-valent silver with a hierarchical nanostructure. X-ray diffraction patterns revealed that layered silver coordination polymer successfully transformed to hexagonal silver upon calcination. According to scanning electron and atomic force microscopy, silver coordination polymer with ~145.5 nm size was homogeneously coated on the surface before calcination, and it evolved micrometer-sized lumps and grooves which were composed of ~58.8 nm sized Ag nanoparticles. The hierarchical structure-micrometer lump/groove consisting of Ag nanoparticles-would be advantageous to kill bacteria; micrometer-grooves provide physical condition (pocket for bacteria capture) and the Ag nanoparticles from the neighboring lump endow chemical condition (antibacterial property of released Ag⁺). The antibacterial activity test on Escherichia coli via colony forming inhibitory assay indeed exhibited an improved antibacterial activity of hierarchical Ag nanostructure compared with the surface simply coated with Ag nanoparticles. From the line profile of atomic force microscopy, the bacterium trapped in the hierarchical Ag nanostructure was shown to interact intimately with Ag surface.