The gas phase reactions of sulphur cluster cations S italicn+ (n = 2,…,8) and anions S italicn− (n = 2,…,6), have been studied by means of a Fourier‐Transform‐Ion‐Cyclotron‐Resonance (FT‐ICR) mass spectrometer. While with several simple gases no reactions, besides some fragmentation, were observed, some of the clusters were found to be reactive towards NO, NH3 and particularly NO2. Where product ions were detected, relative and absolute rate constants were extracted from the data, while only upper limits could be estimated for those systems which do not yield observable amounts of products. We discuss in most detail the reactions of NO2 which reacts with both the anions and cations. By comparing the reactivities of clusters of differing charge we try to deduce the influence of charge versus structure.