A copper foil structure having blackened ultra-thin copper foil of the instant disclosure includes a carrier foil, a blackened layer, a release layer, and an ultra-thin copper foil. The carrier foil includes a matte surface and a shiny surface wherein the blackened layer is disposed thereon. The release layer is disposed on the blackened layer formed with one selected from the group: copper, cobalt, nickel, and manganese while the release layer is formed with one selected from the group: molybdenum, nickel, chromium, and potassium. Successively, the ultra-thin copper foil is disposed on the release layer. Laser drilling can apply to the blackened ultra-thin copper foil on the inner layers of a high density multi-layer printed wiring board, thus eliminating the traditional blackening or browning chemical process. The blackened ultra-thin copper foil in combination with a polyimide thin (PI) or other substrate materials displays desirable appearance.