This essay investigates an additive manufacturing technique of an extruded 3D printing-assisted electrochemical deposition. The effects of solutions with different additive (Cl− and brightener) concentrations on the surface micromorphology and deposition rate of the formed films were investigated by using characterization data from test tools such as an electrochemical workstation, X-ray diffractometer, and scanning electron microscope, as well as discussing the laws of interaction between these two additives during the electrodeposition process. The experimental results show that when the concentration of Cl− in the copper plating solution is 2×10−3 mol/L and the brightener concentration is 10 ml/L, the electrodeposition experiments yielded deposited copper films with a significantly preferred orientation on the (111) crystal plane, and the prepared copper film has thicker deposited film and better surface quality. To validate the additive manufacturing method for extruded 3D printing-assisted electrochemical deposition, deposition experiments of 25-layer copper samples were carried out utilizing the best process parameters.