Pyrrolizidine alkaloids (PAs) are naturally occurring plant toxins with significant multi-organ toxicity, especially hepatotoxicity. Accidental consumption of PAs-containing herbal medicines can lead to severe health consequences, emphasizing the need for rapid and effective detection methods to ensure medicinal safety. In this study, we developed a novel on-site rapid analytical method using paper capillary spray miniature mass spectrometry (PCS-mini MS), and created a database containing 34 different PAs with a detection limit ranging from 0.5 to 2 ng mL^-1. This method is particularly suitable for identifying PAs in herbal medicines, the accuracy of PCS-mini MS was validated through high-performance liquid chromatography-mass spectrometry. Furthermore, the method's environmental impact was assessed using three green evaluation tools, demonstrating its compliance with green analytical chemistry principles, highlighting both efficiency and sustainability. This study provides a convenient and precise approach for regulating the herbal medicine market, enabling quick identification of toxic plants and reducing the risk of adverse health effects from herb misidentification. In the future, this method is expected to be widely adopted for clinical applications and market regulation of herbal products.