The responses of periphytic biofilm to CeO2 nanoparticle (CNP) exposure were explored by investigating community shifts and pollutant removal. Results showed that CNPs entered the sensitive microbial cells in the periphytic biofilm, leading to cytomembrane damage and intracellular reactive oxygen species (ROS) generation. The periphytic biofilm communities were, however, able to adapt to the prolonged exposure and maintain their pollutant removal (i.e., phosphorus, nitrogen and copper, organic matter) performance. Observations under synchrotron radiation scanning transmission X-ray microscopy revealed that fewer CNPs were distributed in algal cells compared to bacterial cells, wherein the transformation between Ce(IV) and Ce(III) occurred. High-throughput sequencing further showed that the proportion of algae, such as Leptolyngbya and Nostoc, significantly increased in the periphytic biofilm exposed to CNPs while the proportion of bacteria, such as Bacilli and Gemmatimonadetes, decreased. This change in community composition might be the primary reason for the sustained pollutant removal performance of the periphytic biofilm. (C) 2017 Elsevier Ltd. All rights reserved.