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Functionalized conjugated microporous polymers (CMPs) containing amino, imino, and hydrazine groups are synthesized by the Sonogashira–Hagihara coupling reaction. Notably, the porosities, thermal stabilities, and morphologies of the CMPs can be controlled by the introduction of functional groups. Here, the relationships between the functional groups and photocatalytic performance are discussed for the first time. The CMP nanowires exhibit excellent photocatalytic performance in organic pollutant degradation: the degradation rate obtained by CMP-I3 bearing naphthalene groups via an imine bond is > 99.99%, and ~ 99.71% of the degradation activity is maintained after five cycles. Notably, the excellent photocatalytic properties of CMP-I3 are imparted by the introduction of the naphthalene groups, which reduced the band gap. The improved charge-transfer activity accounts for the highest and lowest photocurrent intensity and resistance achieved, respectively. Furthermore, the photocatalytic mechanism of CMPs reveals that the superoxide anion is the main active substance in the photocatalytic degradation of dyes. [ABSTRACT FROM AUTHOR]