Sulfonated mesoporous polydivinylbenzene solid acid was prepared by in situ sulfonation method, and the physical chemical properties of this solid acid was characterized by XRD, BET, FT‐IR, etc. Acid density of sulfonated mesoporous polydivinylbenzene was characterized by acid base titration, and the result showed that the acid density was 1.58 mmol H+/g. The condensation of phenol and acetone was used as a probe reaction to investigate the catalytic performance of sulfonated mesoporous polydivinylbenzene as a solid acid. Results showed that the phenol conversion rate could approach theoretical conversion rate with Bisphenol‐A selectivity of 91 % at 90 °C. More importantly, sulfonated mesoporous polydivinylbenzene had good stability, and after repeated use for five times, the catalytic performance was not significantly reduced.