Besides being a luminescent material, cytidine 5'-monophosphate-capped gold nanoclusters (AuNCs@CMP) also show superior peroxidase-like activity which can promote TMB oxidation in the presence of H2O2, causing the solution to turn efficiently from pale to blue. However, the presence of perfluorooctane sulfonate (PFOS) in the above system inhibited TMB oxidation and bluing of the solution, consequently establishing a colorimetric platform of AuNCs/H2O2/TMB for PFOS determination. The results showed that it responded to PFOS over a wide range of 2.0-50 μM, with a limit of detection (LOD) as low as 150 nM. Furthermore, in-depth mechanism investigation revealed that, rather than the active site of the catalyst being occupied by PFOS, such a hypochromatic effect originated from depletion of the reactive oxygen species (ROS) by PFOS degradation, thereby also offering a unique strategy to scavenge the lethal toxicity of PFOS. In addition, the colorimetric response of AuNCs/H2O2/TMB to PFOS was extended to smartphone determination conveniently based on RGB values. Finally, the established platform was applied to PFOS determination both in soil extracts and in tap water with good recovery, which supplies a novel colorimetric platform for visual determination of PFOS in practice. The method has the advantages of being rapid, sensitive and highly selective, which highlight the design and construction of more systems for determination and elimination of lethal pollutants in environmental water.