The photoelectron spectra and the X-ray emission bands of some Cu and Zn ternary compounds were measured. The upper part of the valence band of the A(II) B(IV) C(V)2 compounds consists of p states of about 8 eV width. The d states of the A(II) component are located at energies 10–11 eV below the Fermi level, and their large hybridisation with the p states and the anion s states shows that calculations of the band structure of these compounds without inclusion of the d states should be considered with caution. In the A(I) B(III) C(VI)2 compounds the d states are located at about 3.5 eV between two p state maxima, which could not be seen in earlier investigations. There is a satellite emission in the Cu Kβ5 band being very sensitive to bonding effects.