Abstract In this thesis, the electronic structure of selected atoms was investigated by means of electron and uorescence spectroscopy. Synchrotron radiation was used to excitate atoms in gas phase. In particular, the photoionization and subsequent Auger decay processes in metal vapours were studied as well as the resonant Auger decay in rare gases. The experimental results were analyzed together with theoretical predictions obtained utilizing the multiconfiguration Dirac-Fock method.