Actual methods for on-site measurement of gaseous concentrations of Semi-Volatile Organic Compounds (SVOCs) at the material surface (y0) are not yet sufficiently developed mainly due to sampling difficulties. These concentrations are the key data to improve knowledge about indoor sources and human exposure to SVOCs. To the end, a specific emission cell coupled to solid-phase microextraction (SPME) was developed. The main challenge with this method is calibration because of very low volatility of SVOCs and static sampling mode. In this study, a generating system of organophosphate flame retardants (OFRs) using polyurethane foam as source combined with an active sampling method with Tenax tubes was proposed as a novel calibration device for SPME-based method. The generating system delivered stable OFR concentrations after 190 hours of operation with a variation not exceeding ±5%. It allowed to obtain robust calibrations for tris-(2-chloropropyl)-phosphate (TCPP) and tri-butyl-phosphate (TBP) measured with the emission cell coupled to SPME-based method, define the optimal sampling requirements and achieve reproducible and accurate measurements of y0 at μg.m-3 level. TCPP and TBP gas-phase concentrations at the polyurethane foam surface (y0) were followed up over more 228 days under controlled temperature conditions. A high stability of these concentrations was observed showing that polyurethane foam acts as a stable and continuous source of organophosphate flame retardants indoors. This novel method should be useful for assessing the dynamic of emissions from indoor sources and potential exposure to SVOCs in indoor environments.