Biopolymer-based flocculants have become a potential substitute for inorganic coagulants and synthetic organic flocculants due to their wide natural reserves, environmental friendliness, easy natural degradation, and high material safety. In recent years, with more and more attention to clean technologies, a lot of researches on the modification and application of biopolymer-based flocculants have been carried out. The present paper reviews the latest important information about the base materials of biopolymer-based flocculants, including chitosan, starch, cellulose, and lignin etc. This review also highlights the various modification methods of these base materials according to reaction types in detail. Via the recent researches, the flocculation mechanisms of biopolymer-based flocculants, such as adsorption, bridging, charge neutralization, net trapping, and sweeping, as well as, some other special mechanisms are comprehensively summarized. This paper also focuses on the water treatment conditions, the removal efficiency, and advantages of biopolymer-based flocculants in applications. Further, this review sheds light on the future perspectives of biopolymer-based flocculants, which may make progress in the sources of base materials, modification processes, multi-function, and deepening application researches. We believe that this review can guide the further researches and developments of biopolymer-based flocculants in the future, to develop them with a higher efficiency, a lower cost, more safety, and multi-function for more diversified applications.