The study is devoted to the detailed investigation of the ipso-chlorination reaction of calixarenes and search of an optimal combination of chlorinating reagents. This factor was varied in a number of experiments. It was established that the presence of sulphuryl chloride and the acidic proton is a necessary condition for successful ipso-chlorination of calix[4]arenes. The addition of any of phosphorus chlorides accelerates reaction speed and increases process yield. So the most promising chlorination mixture was that SO2Cl2 (4 eq.), POCl3 (1 eq.) and glacial acetic acid (1 eq.) which provided 64% yield of the desired compound after two days of the experiment.