The measurement of K shell fluorescence parameters is an easy and practical way to investigate the electronic structures of elements in alloys, compounds or complexes. Since the number of valence electrons will change the screening effect, the measured parameters will be affected from the changes. In this study, the measured parameters were investigated for sulphur element according to the number of CH2 groups. For the experimental measurements, the samples were excited by 59.5 keV γ rays from a 241Am annular radioactive source. The emitted K X-rays from the samples were counted by ab Ultra-LEGe detector with a resolution of 150 eV at 5.9 keV.