The work aims to prepare the microstructure on free-curved surfaces of metal workpieces. A novel process to prepare colloidal particle mask on curved surfaces of metal workpiece by interface transfer method and fabricate micro-dimple array between colloidal particles by electrodepositing process was proposed. The monolayer colloidal particle mask could be formed on the curved surface of the metal workpiece by the interface transfer method. The micro-dimple array with a good uniformity was obtained by electrodepositing at current density of 0.3 A/dm2 for 20 min after the removal of the colloidal particle mask, and the diameter of single micro-dimple was about 3.4 μm. After electrodepositing for 20 min at current density of 0.3 A/dm2, the diameter of micro-dimples increased with the prolongation of the electrodepositing time, and the hydrophobicity of the deposited layers increased firstly and then decreased with the increase of the micro-dimple diameter. The deposited layer with best hydrophobicity was obtained when the diameter of the micro-dimple was about 5 μm, and the contact angle on the cylinder surface was about 120°. Micro-dimple array on the curved surface of the metal workpiece can be obtained by electrodeposition process with the colloidal particle mask formed by the interface transfer method. The deposited layer with the micro-dimple array is the hydrophobic surface. The micro-dimple array with the good hydrophobicity can be obtained by adjusting the electrodepositing time and the current density.