Delafossite CuAlO 2 has great potential in optoelectronics applications. The intrinsic point defects play the decisive roles in the optoelectronic properties and application of CuAlO 2 . However, there are still disputes about their relevant underlying physical mechanisms at the atomic scale. Here, the formation of intrinsic point defects of CuAlO 2 and their effects on optical absorption spectra and electronic structure have been systematically investigated using firstprinciples calculations. In oxygen-rich and oxygen-poor chemical environments, acceptor-type defects such as Cu vacancy and Cu substitution on the Al site can spontaneously form and produce p-type conductivity at room temperature. This is the important physical basis for CuAlO 2 to be widely used as transparent conductive oxide films. The shallow acceptor-type levels produced by Cu substitution on Al site and O vacancy, and the shallow donor-type levels pro-How to cite this article: Zhao Z-Y, Zhang J-X, Chen X-L. New insights into intrinsic point defects of delafossite CuAlO 2 as optoelectronic materials. J