This Article reports on gradient electrodeposition of copper on the surface of a bipolar electrode (BPE). The formation mechanism of the as-fabricated gradient nanostructure is discussed, and the effects of time, potential, and concentration of CuSO4 solution on the morphology of the deposited structures are investigated. Scanning electron microscopy (SEM) is used to visualize the morphology of the deposited Cu at different positions of the BPE. By scanning from the cathodic pole to the midpoint of the BPE, three distinct structures are observed; (i) nanodendrites, (ii) nanodendrites in the vicinity of nanoparticles, and (iii) nanoparticles. The BPE surface was characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements. The contact angle measurement of a water droplet reveals a surface with gradient wettability. Modification of the as-electrodeposited Cu surface with 1-dodecanethiol provides self-movement of the water droplet.