In this study, the extracellular polymeric substance of Scenedesmus quadricauda called EPS-S.q and its bioflocculatoin mechanism were investigated. Results showed EPS-S.q was successfully used as bioflocculating agent for S. quadricauda biomass harvesting and flocculation efficiency of up to 86.7% to S. quadricauda cells could be achieved in presence of Zn2+. EPS-S.q was the flocculating agent for self-flocculating microalga S. quadricauda and bioflocculation mechanism was polymer bridging. The sugar and protein mass fraction of dry EPS-S.q was sugar 56.7% and protein 41%. The infrared spectrum further indicated the presence of hydroxyl, carboxyl and amino groups. Moreover, pH decrease induced the flocculation of S. quadricauda and 78.4% of flocculation efficiency was the highest at pH 3. In addition, chemical flocculant FeCl3 was efficiently used for S. quadricauda harvesting and up to 96.8% of flocculation efficiency could be achieved for S. quadricauda culture with biomass concentration 0.21-0.39 g L-1 at pH 7. (C) 2016 Published by Elsevier Ltd.