The microstructure at the interface of diffusion-bonded joints of oxygen-free high-conductivity copper for two kinds of surface conditions, with and without argon ion bombardment treatment, was investigated using scanning and high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy. The results showed that argon ion bombardment effectively removed the surface oxide film layer and lowered the height of the surface asperity, so that inclusion formation was decreased and void shrinkage time was shortened at the interface of the bonded copper joints, and the tensile strength of diffusion-bonded copper joints was improved obviously.