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Ultrafine copper powder with uniform morphology and size was synthesized by electrodeposition. By using the Box‐Behnken design of response surface methodology, to study the interaction between anionic surfactants and nonionic surfactants at different concentrations of copper sulfate pentahydrate. The resulting copper powder was characterized by scanning electron microscopy. The results show that it is difficult to obtain uniform copper powder by using a single anionic surfactant. The staggered adsorption mechanism of the non‐ionic surfactant and the anionic surfactant at the interface disperses and stabilizes the micellar interface and prevents continued growth of the copper powder. The resulting copper powder is nearly spherical with uniform morphology and particle size. Through the optimization of the response surface methodology, a nearly spherical copper powder with an average particle size of 0.61 μm and uniform shape was finally obtained. [ABSTRACT FROM AUTHOR]