he reactions of phenoxathiin radical cations with diverse organic compounds in ambient conditions were realized by using fused-droplet electrospray ionization mass spectrometry. In the investigation, the phenoxathiin radical cation was prepared by electrospray ionization. The reactants included aliphatic alcohols, phenol and phenyl halides and the reaction studies showed the unique reactivity the of phenoxathiin radical cation towards neutral organic compounds in ambient conditions, which has not been revealed in previous studies.