The influence of algal organic matter (AOM) on the settling performance of algal flocs remains poorly understood. To address this, we employed fractionation techniques based on molecular weight to isolate different AOM fractions and analyzed their effects on floc structure and settling performance. This involved comparing the concentrations, compositions, potentials, and functional groups of organic matter before and after coagulation-sedimentation. The results demonstrated that AOM significantly impacts floc characteristics, including size and compactness, ultimately hindering floc settling performance. Specifically, AOM fractions smaller than 100 kDa, such as humic substances, preferentially consumed coagulants without directly participating in floc formation, leading to smaller and slower-settling algal flocs. This was particularly evident for fractions with a molecular weight below 5 kDa, where only 25 % of the material participated in floc formation. In contrast, over 90 % of the AOM with a molecular weight exceeding 100 kDa, such as proteins, exhibited negatively charged functional groups (e.g., carboxyl groups) that interacted with coagulants via electrostatic forces to form larger complexes. These complexes enhance the coagulant's ability to capture and bridge algal cells, directly binding to the flocs, resulting in an increase of 20.3 % in the size and a 37.5 % faster settling velocity of the flocs formed by >
100 kDa AOM compared to <
5 kDa. This study elucidates the mechanisms by which AOM influences algal floc settling performance from the perspectives of AOM composition and its interactions with coagulants and algal cells. The findings provide a theoretical basis for a deeper understanding of algal flocculation mechanisms and for accelerating algal flocculation and sedimentation.