The electronic structure of TlCo2Se2 has been investigated by means of band structure calculations and x-ray photoelectron and emission spectroscopy (XPS and XES). The formation of the valence band is described in connection with calculations of partial densities of states of the valence band and Co Lα,β x-ray emission () aligned to the binding energy scale. The experimental results are in agreement with the calculated distribution of Co 3d states, which lie close to the Fermi level. The effect of Co–Se bonding is seen as satellite structures in the XPS Co 2p signals. Thermoelectric and Hall effect data as well as resistivity measurements show that TlCo2Se2 is metallic with electron holes as charge carriers with broadband mobility characteristics. The observed anisotropy of the resistivity in the ab plane and along c remains constant as a function of temperature, i.e. without signs of the magnetic ordering that occurs (TN~85 K). The results of local spin density functional calculations show ferromagnetic coupling within the cobalt plane as a result of direct magnetic interactions between the magnetic moments.