Volatile organic sulfur compounds (VOSCs) pose serious threats to environment and human health, while detection techniques of VOSCs are expensive and complex. Here, this paper first-time reported a hydrogen-bond acidic (HBA) polymer-based surface acoustic wave (SAW) chemical sensor for the detection of four VOSCs (methyl mercaptan, dimethyl sulfide, dimethyl disulfide, and carbon disulfide). The results show that this sensor exhibited both excellent sensitivity (limit of detections ranging from 0.035 to 0.11 mg/m3) with fast response and recovery and high selectivity (2.23–49.6 times higher response than interference vapors) toward VOSCs at room temperature. The good performance is attributed to the hydrogen bonding between the sulfur atom of VOSCs and hydrogen atom of hexafluoroisopropanol (HFIP) groups in polymer chain. Fourier-transform infrared spectroscopy (FTIR) spectrum and first principle calculations were performed to further support this proposed mechanism.