Microcystin-LR (MC-LR), the most common algal toxin in freshwater, poses an escalating threat to safe drinking water. This study aims to develop an engineered biofiltration system for water treatment, employing a composite of poly(diallyldimethylammonium chloride)-biochar (PDDA-BC) as a filtration medium. The objective is to capture MC-LR selectively and quickly from water, enabling subsequent biodegradation of toxin by bacteria embedded on the composite. The results showed that PDDA-BC exhibited a high selectivity in adsorbing MC-LR, even in the presence of competing natural organic matter and anions. The adsorption kinetics of MC-LR was faster, and capacity was greater compared to traditional adsorbents, achieving a capture rate of 98% for MC-LR (200 μg/L) within minutes to tens of minutes. Notably, the efficient adsorption of MC-LR was also observed in natural lake waters, underscoring the substantial potential of PDDA-BC for immobilizing MC-LR during biofiltration. Density functional theory calculations revealed that the synergetic effects of electrostatic interaction and π-π stacking predominantly contribute to the adsorption selectivity of MC-LR. Furthermore, experimental results validated that the combination of PDDA-BC with MC-degrading bacteria offered a promising and effective approach to achieve a sustainable removal of MC-LR through an "adsorption-biodegradation" process.