A convenient, efficient and practical approach for the synthesis of S-quinolyl phosphorothioates via cheap TsCl promoted deoxygenative C2-H phosphorothiolation of quinoline N-oxides with readily available triethylammonium O,O-dialkylphosphorothioates was developed. The reaction performed well under transition-metal-free conditions at room temperature with a very short reaction time (10-20 min). Preliminary studies showed that the current transformation underwent a nucleophilic substitution process.