Detoxification of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with high efficiency and dynamic performance is challenging for a polymeric catalyst. Herein, a series of conjugated microporous polyanilines (CMPAs), capable of efficiently catalytically reducing 4-NP, were synthesized based on the Buchwald−Hartwig cross-coupling reaction mechanism. By adjusting the types of linkers and the molar ratios of linker to core, CMPAs with different Brunauer−Emmett−Teller (BET) specific surface areas and reduction degrees were obtained and used as the catalysts in reducing 4-NP. The ultrahigh catalytic reduction efficiency (K = 141.32 s −1 g −1 , k app = 0.00353 s −1 ) was achieved when using CMPA-3-0.7 as the catalyst (prepared with 4,4′-diaminodiphenylamine as the linker and a 0.7:1 molar ratio of linker to core). The catalytic reduction performance exhibited a strong correlation with the reduction degree and BET specific surface area of CMPAs. Furthermore, they also exhibit excellent cycling stability and dynamic performance. The coexistence of a microporous structure and high BET specific surface area endowed CMPAs with an increased number of catalytic active centers. The reversible redox transformation of CMPAs in the presence of NaBH 4 and air enabled selfhealing (the oxidation units in CMPAs were reduced to reduction units by NaBH 4 , and the newly generated reduction unit in CMPAs was subsequently oxidized to its original state by the O 2 in the air), leading to the reduction reaction of 4-NP proceeded continuously and stably. The aforementioned factors resulted in the high efficiency of CMPAs for reducing 4-NP to 4-AP, enhancing the practical application prospects of CMPAs in the detoxification of 4-NP wastewater.