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The efficient and green removal technology of refractory organics such as atrazine in water has been an important topic of research in water treatment. A novel membrane composite biocatalyst Lac-HBT-Pd/BC as prepared for the first time by co-immobilizing laccase, mediator 1-hydroxybenzotriazole (HBT) and metal Pd on functionalized bacterial cellulose (BC) to investigate the removal of atrazine and degradation of its intermediates under mild ambient conditions. It was found that atrazine could be completely degraded in 5 h by the catalysis of Lac-HBT-Pd/BC, and the removal rate of degradation intermediates from atrazine was about 85% after continuous catalysis, which achieved deep degradation of atrazine. The effect of electrochemical activity and radical stability of the membrane composite biocatalysts loaded with Pd was investigated. The possible degradation pathways were proposed by identifying and analyzing the deep degradation products of atrazine. The Lac-HBT-Pd/BC demonstrated deep degradation of atrazine and favorable reusability as well as considerable adaptability to various water qualities. This work provides an important reference for preparing new kinds of biocatalysts to degrade refractory organic pollutants in water., Competing Interests: Declaration of Competing Interest There are no known competing financial interests or personal relationships., (Copyright © 2024. Published by Elsevier B.V.)