Cyanobacterial blooms can cause serious damage to aquatic ecosystems. However, we have demonstrated that typical algae-blooming species Microcystis aeruginosa (M. aeruginosa) combined with photocatalysts could synergistically facilitate the photodecontamination of tetracycline hydrochloride (TC) and Cr(VI). In this study, for the first time, harmful algae were successfully converted into photoreactive bionano hybrid materials by immobilizing M. aeruginosa cells onto polyacrylonitrile (PAN)-TiO₂/Ag hybrid nanofibers, and their photocatalytic activity was evaluated. The addition of M. aeruginosa significantly improved the photodecontamination, and the reaction rate constant (k) values of TC and Cr(VI) degradation by M. aeruginosa-PAN/TiO₂/Ag nanofiber mats were 2.4 and 1.5-fold higher than that of bare PAN/TiO₂/Ag nanofiber. Photoreaction caused damage to algae cells, but no microcystin was found that had been photodegraded simultaneously. The effects of various active species were also investigated, and the photodegradation mechanism was proposed. Recycling tests revealed that this flexible M. aeruginosa-PAN/TiO₂/Ag hybrid mat had potential application in the removal of mixed organic and inorganic pollutants with high efficiency and without secondary pollutants. Thus, harmful algae blooms could serve as an efficient materials to remove toxic pollutants in a sustainable way under visible light irradiation.