In order to accurately analyze trace-level, reduced sulfur compounds (RSC) in ambient air, one needs to rely on the thermal desorption technique (TD) to atone for the limited sensitivity of direct gas chromatography (GC) analysis. In this study, the relative performance of GC/PFPD system combined with TD unit was evaluated to help accurately determine RSC based on the comparative analysis of two types of calibration approaches. Hence, calibration results of RSCs were compared by controlling sample transfer system (air server (AS) and TD unit) between the two contrasting calibration approaches such as: incremental-loading of a given standard with the fixed standard concentration (FSC) vs. supply of standards made at multiple concentration points at the fixed standard volume (FSV). The results of our study indicate that RSC calibration is affected fairly sensitively by sample loading conditions of the AS/TD system. It is hence necessary to delicately control the TD operation conditions for the accurate quantification of RSCs, when GC/PFPD system with TD is employed for RSC analysis.