Abstract: In this paper, we report that silver filaments are self-assembly obtained on solid substrate with a unique method of electrodeposition through mixed solution of AgNO3 and H3PO4. The electrodeposits have finger-like morphology and are composed of large quantity of small flakes. The result of energy dispersive spectrometer (EDS) demonstrates that deposits are silver. The crystal information of silver flake is analyzed with a high-resolution transmission electron microscope (HRTEM). The mechanism of phosphoric acids in the process of silver flakes electrodeposition is also discussed.