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The surface of gold nanorods is chemically charged by ascorbic acid; the charging effect results in not only the blue shift on their surface plasmon bands, but also the change of the deposition rate of silver on their surfaces. The rate was prominently accelerated at room temperature, but slightly slowed down at higher temperature. The shape of gold‐silver core‐shell nanoparticles could not be obviously affected. The Fermi level of gold nanorods begins to increase under the action of charging and alters the electrical double‐layer structure of gold nanorods, resulting in the different deposition rate of silver on gold. [ABSTRACT FROM AUTHOR]