Secondary ion mass spectrometry (SIMS) was used to study the near-surface segregation of sulphur during; (a) the thermal processing stages (diffusion annealing after application of Pt bond coat and after secondary ageing following subsequent deposition of the Y2O3-stabilised ZrO2 top coat) and (b) thermal cycling in the Ni-base superalloy, CMSX4. In the thermal processing stages, an increased segregation of sulphur was observed within the upper regions of the Pt bond coat after diffusion annealing, while following secondary ageing, the sulphur segregation in this layer became heterogeneous with discrete pockets of enrichment (≫1 ppm) and regions of depletion (≪1 ppm). During thermal cycling, partitioning of sulphur occurred to the Pt-enriched γ′ region characterised by the finger-like morphology, while examination of TBC spalled specimens showed significant depletion of sulphur within the substrate in the vicinity of the surface. The reservoir for sulphur-depletion within the substrate was definitively identified as the Pt-enriched γ′ region. A quantitative method for the calculation of sulphur-segregation at the surface in terms of mono-layers is presented.