Abstract: The excessive residual concentrations of volatile organic compounds (VOCs) in textiles pose a significant threat to human health, making their detection a critical aspect of textile quality control. Conventional detection methods, as stipulated in existing standard protocols, often involve complex sample pretreatment procedures, are time-consuming, and offer low throughput, rendering them inadequate for the rapid and large-scale screening required in modern manufacturing and regulatory oversight. To address these limitations, a novel rapid screening method based on proton transfer reaction-mass spectrometry (PTR-MS) was developed in this study. The core work focused on the design and integration of a dedicated sampling device into a PTR-MS analysis system. This specialized sampling apparatus was engineered to facilitate the direct and efficient transfer of VOCs emitted from textile samples into the PTR-MS ion source. The PTR-MS system allows for the sensitive and selective detection of a wide range of VOCs without significant fragmentation. Crucially, the entire methodology operates without the need for sample pre-treatment steps such as extraction or concentration, which are typical bottlenecks in traditional techniques (e.g., GC-MS). Furthermore, key operational parameters, including system cleaning time, carrier gas flow rate, effective sampling area, and sample heating temperature, were systematically optimized to ensure stable, efficient, and reproducible analysis. Experimental validation demonstrated the outstanding performance of the proposed method. It achieved detection limits as low as 0.01 to 0.50 mg/kg for typical harmful VOCs in textiles, including formaldehyde and benzene homologues (e.g., benzene, toluene, ethylbenzene, xylenes). The method exhibited excellent linearity over the relevant concentration ranges. Notably, the quantitative analysis of formaldehyde in textiles yielded a relative error of only 6.20%, which highlights its accuracy even under rapid analysis conditions. The most significant result is the marked reduction of analysis time, with the complete spectral analysis of VOCs from a single textile sample accomplished in less than 1 min. This represents a substantial improvement over conventional methods, which can take from several minutes to hours per sample. By eliminating pre-treatment and reducing analysis time to under 1 min per sample, this PTR-MS-based method significantly enhances detection throughput and operational efficiency. It provides a reliable and practical solution for the rapid, large-scale screening of VOCs in textiles, a capability that is increasingly demanded by quality control laboratories, regulatory bodies, and textile enterprises managing extensive supply chains. The method’s ability to perform rapid, full-spectrum screening also opens new avenues for non-targeted analysis and the discovery of unexpected or emerging VOC contaminants in textile products. Despite its promising advantages, it is important to acknowledge the current limitations of this study. The primary limitation is that validation was performed under controlled laboratory conditions using a limited set of textile samples. The method's performance and robustness in real-world, large-scale batch screening scenarios have not yet been empirically demonstrated.