In this letter we describe a novel but effective wet-chemical route for the simple preparation of snowflake-like dendritic nanostructures of Ag, which are homogeneous in size, carried out by directly mixing AgNO3 and p-phenylenediamine (PPD) aqueous solutions at room temperature. It reveals that such dendrites are aggregates of nanoparticles and highly crystalline in nature. It is found that the molar ratio of [PPD]/[Ag+] influences the final morphologies of the structures formed and that excessive PPD (the molar ratio of [PPD]/[Ag+] is higher than 1:1) is crucial to achieving dendrites. The possible dendritic growth mechanism is also predicted. This method can also be extended to the preparation of Au dendrites.