High intensity of synchrotron radiation improves significantly possibilities of photoluminescence observation and allows us to observe photoluminescence (PL) of CoO for the first time. As soon as no experimental photoluminescence excitation (PLE) spectra in the region of interband transitions for CoO are described in the literature, the preliminary results are interpreted in comparison with the PL and PLE spectra of NiO. Difference between obtained PLE spectra of CoO and PLE spectra of NiO is small. Therefore we expect similar structure of the valence band states for CoO and NiO. Further detailed analysis of PL and PLE spectra of CoO on the basis of cluster model is required.