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The pernigraniline (PNA)/TiO₂ composite film has been synthesized by the combination of hydrothermal and electro-polymerization methods. The as-prepared PNA/TiO₂ composite film was characterized by XRD, SEM, FTIR and XPS as well as photocatalytic degradation of Rhodamine B (RhB). And the roles of actives species in the photocatalytic process were investigated by using different types of active species scavengers. It was found that PNA/TiO₂ film was reduced towards to the emeraldine (EM)/TiO₂ in the photocatalytic reaction process and the roles of actives species in PNA/TiO₂ system were different to EM/TiO₂ system. The enhanced photocatalytic performance was attributed to that the PNA acted as the electrons acceptor, which was favorable for the separation of the photoinduced electron–hole pairs and could enhance the activity of the photocatalysts.

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