First systematic study of satellites in x-ray emission spectra was performed by Deslattes using quasi-monochromatic photon excitation from a group of L{alpha} x-ray sources lying close to the K edge of Cl. He observed significant alterations in the Cl K{beta} spectrum of KCl depending on the character of the excitation radiation and identified the initial state of these satellites as a double vacancy state. Recently, the valence electronic structure of the chlorofluoromethanes were analyzed by chlorine K x-ray emission under satellite-free conditions. These studies were based on the use of synchrotron radiation to eliminate the multivacancy effects that are inherent in conventional x-ray spectroscopy. In this report, satellite free x-ray emission spectra from chlorofluoromethanes will be presented to demonstrate that the simplified spectra can be obtained using selective photon excitation. Results from various research groups world wide, utilizing the tunable photon excitation form synchrotron sources to eliminate the obscuring features in x-ray emission spectra of rare-gas solids (RGS) and metals will be discussed. Also, the technical challenges in utilizing the small phase-space attributes of high brightness from third generation SR sources producing x-ray and vacuum ultra-violet wavelengths to study weak features like satellites in x-ray emission spectra will be presented