Resonant photoemission of single crystals of the perovskite TbBaCoO3 has been carried out for freshly scraped surfaces. The resonance onset energy at the Co3p→3d threshold is used to explore the contribution of Co3d electrons to the electronic structure of the valence band. The Energy Distribution Curves (EDC) corresponding to the valence band of the crystal were determined for radiation energies hv in the region of hv=60 eV. For 63.2 eV binding energy, the main contribution of Co 3d electrons was found in the main valence band peak located at 7.46 eV below the Fermi level, whereas the contribution of Tb4f electrons was found at energy 12.08 eV below the Fermi level. The results show that the density of states close to the Fermi energy is of Co3d/O2p character, with any Tb4f contribution.