Fischer-Tropsch synthesis (FTS) is commonly viewed as an alternative approach to the production of diesel fuels via sources independent of crude oil. The adaptability of the FTS process allows for the selective production of shorter chain C-2 to C-6 hydrocarbons and has the potential to be a legitimate source of useable chemical feed-stocks with high value to the chemical manufacturing industry. Interestingly, although recognised as a poison in most catalytic systems, small amounts of sulfur in iron-based FTS catalysts has been demonstrated to promote catalyst reducibility and activity towards shorter chain hydrocarbons. However, it is not known what impact sulfur has on the formation of hydrocarbonaceous surface species that have been proposed to play a pivotal role in the mediation of reactants during iron FTS. Here we apply ambient pressure CO hydrogenation at 623 K on a selection of sulfur promoted iron FTS catalysts to investigate the effect of sulfur content on hydrocarbonaceous species formation. For the first time, we report the application of inelastic neutron scattering to quantify the presence of hydrocarbonaceous species under the presence of sulfur promotion. In combination with temperature programmed oxidation, X-ray diffraction, and Raman spectroscopy, we observe how low sulfur loadings ( < 700 ppm) perturb carbon and hydrogen retention levels. The results indicate that the presence and nature of the hydrocarbonaceous overlayer is sensitive to sulfur loading, with the reported loss in catalytic activity at high loadings correlating with the attenuation of hydrocarbonaceous surface species.