The electronic structures of organic salts (DI-DCNQI)(2)M with M = Cu and Ag, where DI-DCNQI is 2,5-diiodo-N,N'-dicyanoquinonediimine, were studied using photoelectron spectromicroscopy at various photon energies. From the photon energy dependence of the photoionization cross-section, the atomic orbital characters of the observed spectral features were determined. For both (DI-DCNQI)(2)Cu and (DI-DCNQI)(2)Ag, the C and N 2p states originating in the cyano group and the quinone ring are located at similar to 4.0 and similar to 6.5 eV, respectively. The Cu 3d states for (DI-DCNQI)2Cu and the Ag 4d states for (DI-DCNQI)(2)Ag are located at similar to 3.2 and similar to 5.2 eV, respectively. This indicates that the p pi-d hybridization at the Fermi level between the M ions and the N atoms of the DCNQI columns is larger for (DI-DCNQI)(2)Cu than for (DI-DCNQI)(2)Ag. The reason for the difference in the electronic structure between (DI-DCNQI)(2)Cu and (DMe-DCNQI)(2)Cu is also discussed. (C) 1999 Elsevier Science Ltd. All rights reserved.