Abstract: The present disclosure provides a detection method of wormlike micelles, and belongs to the technical field of analytical chemistry. In the present disclosure, z-ArN2+ is used as a chemical probe substance; a long-chain probe is added to a test solution for probing an interfacial region, and a short-chain probe is added to a surfactant-free control solution. A selectivity of the probe with different nucleophiles is determined by the above method, and a yield of an obtained product is measured by high-performance liquid chromatography (HPLC); and the wormlike micelles are detected by measuring the yield of the product using the selectivity of the short-chain probe to be converted into an interfacial mole number. The wormlike micelles are detected by chemical probes, and the chemical probes have a simple preparation method, a low cost, real-time detection, and broad prospects for use.