Photocatalysis has attracted much attention as an emerging algae removal technology, but the inactivation performance is inevitably affected by the extracellular polymeric substance (EPS) produced by algae. In this study, a photocatalyst (Ag2O/g‐C3N4) with efficient algae inactivation is adopted to investigate the interactions with EPS, and the impact of EPS on photocatalytic algae removal is studied. The results show that EPS can adhere to the surface of Ag2O/g‐C3N4 by electrostatic force. The interaction with EPS decreases the surface zeta potential of the Ag2O/g‐C3N4 from 7.71 to −22.3 mV with the increase in EPS concentration, and the maximum ratio of particle size increases from 825 to 1281 nm. In addition, the interaction with EPS inhibits the release of Ag+ in Ag2O/g‐C3N4 by half, thus, the toxicity of metal ions will be alleviated. Meanwhile, EPS can also be degraded by Ag2O/g‐C3N4, indicating that EPS can work as a radical scavenger to protect the algae cells. Without the protection of EPS, 97.8% of algae cells are inactivated after 5 h photocatalysis. Therefore, more attention should be given to the interaction between EPS and photocatalyst to promote the design and application of the photocatalytic.