Accurate low-order structure factors for copper metal have been measured by quantitative convergent beam electron diffraction (QCBED). The standard deviation of the measured structure factors is equal to or smaller than the most accurate measurement by any other method, including X-ray single crystal Pendellösung, Bragg γ-ray diffraction, and high-energy electron diffraction. The electron structure factor for the (440) reflection was used to determine the Debye-Waller (DW) factor. The local heating of the specimen by the electron beam is determined to be 5 K under the current illumination conditions. The low-order structure factors for copper measured by different methods are compared and discussed. The new data set is used to test band theory and to obtain a charge density map. The charge deformation map shows a charge surplus between the atoms and agrees fairly well with the simple model of copper 2+ ions at the atomic sites in a sea of free uniformly distributed electrons.