In this paper, using p⁃tert⁃butylphenol and sulfur as raw materials, the p⁃tert⁃butylthiacalix[4]arene was first synthesized under alkaline conditions, and then thiacalix[4]arene sulfonic acid was obtained by reacting with concentrated sulfuric acid. The nitration of toluene was catalyzed by thiacalix[4]arene sulfonic acid as catalyst. In the nitration of toluene, the effects of the molar ratio of toluene to nitric acid, the amount of catalyst, the reaction time and the reaction temperature on the nitration of toluene were investigated. The catalyst recovery and reuse experiments were carried out. The results showed that when n(toluene)/n(nitric acid) was 1∶4, the catalyst mass was 0.100 g, and the reaction was carried out at 80 ℃ for 6 h, the conversion of toluene was 98.0%, the ratio of o⁃para⁃nitrotoluene was 1.3, and the catalyst can be reused 4~5 times.