Abstract The defect structure of CuMX2 (MºIn, Ga and XºS, Se, Te) was investigated. The defect concentrations were derived as a function of nonmolecularity( X) and nonstoichiometry( Y), and the carrier concentrations were calculated quantitatively using a theoretical defect model, which could be used to select the proper region of stoichiometry for device designs with specified carrier concentrations. The compensation reaction between dopants and intrinsic defects in CuMX2, compound semiconductors is quantitatively illustrated. If for a small increment of temperature the Fermi level EF is shifted by £GEF and the concentration of free majority carriers is increased by £Gn, then the ratio£Gn /£GEFis a measure of the defect-level concentration within£GEF. The electrical and optical properties of CuMX2 have been investigated using various types of electrically active intrinsic defects caused by deviations from the ideal stoichiometry of the compound. The defect complexes are formed by reactions among the impurity and native defects and/or among the native defects during crystal growth or during processing, and play a significant role in determining the characteristics and performance of devices by affecting lifetimes, degradation and breakdown etc.