We study nanometer copper thin films prepared by magnetron sputtering and treated with laser shock processing (LSP). We observe the formation of firstborn twin crystals and some complete twin crystals in the copper thin films. After LSP, scanning electron microscope (SEM) images show obvious plastic deformation of the copper grain on the film surface, dramatically increased grain size, and the appearance of a large number of twin crystals. Moreover, the width of the crystals is a few dozen nanometers, and the cross angle is more than or close to 90o. Many vacancy defects appear during the sliding of atomic plane, which leads to a faulty structure; however, no obvious dislocation is observed. These substructures play a significant role in improving the mechanical performance of nanometer copper thin films.