The electron scattering at surfaces, interfaces, and grain boundaries is investigated using polycrystalline and single-crystal Cu thin films and nanowires. The experimental data is described by a Fuchs-Sondheimer (FS) and Mayadas-Shatzkes (MS) model that is extended to account for the large variation in the specific resistivity of different grain boundaries as well as in situ anneal and a subsequent etch to match the thickness of the SG samples. Nanowires are fabricated from the SG and LG thin films using a subtractive patterning process, yielding wire widths of 75-350 nm. Single-crystal and LG layers exhibit a 18-22% and 10-15% lower resistivity than SG layers, respectively. The resistivity decrease from SG to LG Cu nanowires is 7-9%. The thickness and grain size dependence of the resistivity of polycrystalline and singlecrystal Cu layers is well described by an exact version of the existing FS+MS model, but is distinct from the commonly used approximation which introduces an error that increases with decreasing layer thickness from 6.5% for d = 50 nm to 17% for d = 20 nm. The case of nanowires requires the FS+MS model to be extended to account for variation in the grain boundary reflection coefficient R, which effectively increases the overall resistivity by, for example, 16% for 50×45 nm 2 wires. The overall data from single and polycrystalline Cu layers and wires yields R = 0.25±0.05, and p = 0 at Cu-air and Cu-Ta interfaces.2