In this study, the analytical bias in the measurements of reduced sulfur compounds (RSC) was investigated in terms of sorptive loss caused by the materials selected for the sample introduction. For the purpose of this study, three vacuum samplers made in the combination of different vacuuming efficiencies (e.g., rapid versus slow sampling) and different materials (i.e., Teflon versus stainless steel (SS)) were tested to evaluate the sampling recovery rate (RR) for five RSCs: H(2)S, CH(3)SH, DMS, CS(2) and DMDS. To make a parallel comparison of RR, the RSC standard samples contained in one bag were transferred to another bag using each sampling system. Their relative contents between, before, and after the transfer were then evaluated between different samplers to assess the sampling bias caused by the interaction between RSC and the sampling material. In the case of the most reactive compound, H(2)S, the sampling loss from the SS inlet line amounted to as high as 45%, while that for the Teflon counterpart was almost insignificant. When the sampling time was arbitrarily elongated (i.e., use of a slow sampler), the sampling loss rate of the SS inlet sampler became more significant with the RR values dropping down from 55 to 70%, across different RSCs. The overall results of our comparative study indicate that the sampling system for the reactive gaseous compounds should be checked for the material feasibility to guarantee sufficient analytical reliability.