The conductivity (i.e., n-type or p-type) of Cu2O films is controlled by the electrodeposition potential. A slightly acidic solution (pH 4.93) containing cupric acetate and sodium dodecyl sulfate (SDS) is used. Photoelectrochemical measurements at zero bias indicate that the Cu2O films deposited at the potentials of 0.00 V and -0.05 V generate the ntype photocurrents and the films deposited at the potentials negative than -0.10 V generate the p-type photocurrents. The X-ray diffraction (XRD) results show that the n-type films are pure Cu2O, however, the metallic copper appear in the ptype Cu2O films. Mott-Schottky measurements show that the donor concentrations of the n-type Cu2O films decrease and the acceptor concentrations of the p-type Cu2O films increase with the decrease of the deposition potential. The SDS molecules adsorbed on electrode surface and the SDS micelles block the diffusion of Cu2+ ions, resulting in a low diffusion rate of Cu2+ ions. Under this circumstance, the growth of Cu2O films are affected significantly by the overpotential. When the potential is positive than -0.05 V, oxygen vacancies are formed in the films leading to the n-type conductivity; however, when the potential is negative than -0.10 V, the Cu2+ ions are reduced to Cu+ rapidly and part of Cu2+ are reduced to metallic copper, the diffused Cu2+ ions to supply to the growth of Cu2O films are insufficient, hence copper vacancies are formed in the films resulting in the p-type conductivity.