The wide application of water-soluble linear polyacrylamides (PAMs) can cause serious environmental pollution. Biological treatment of PAMs receives very limited efficiency due to their recalcitrance to the microbial degradation. Here, we show the bioelectrochemical system (BES) can be used as an effective strategy to improve the biodegradation efficiency of PAMs. A linear PAM with viscosity-average molecular weight of 5 x 10(6) was treated in the anodic chamber of BES reactor, and the change of PAM structure during the degradation process was investigated. The anodic bacteria in the BES demonstrated abilities to utilize the PAM as the sole carbon and nitrogen source to generate electricity. Both the anode-attached and planktonic bacteria contributed to the electricity generation, while the anode-attached community exhibited stronger electron transfer ability than the planktonic one. The closed-circuit and open-circuit operations of the BES reactor obtained chemical oxygen demand (COD) removal efficiencies of 32.5 and 7.4 %, respectively, implying the generation of bioelectricity could enhance the biodegradation of PAM. Structure analysis suggested the carbon chain of PAM was partially degraded in the BES, producing polymeric products with lower molecular weight. The microbial cleavage of the carbon chain was proposed to start from the "head-to-head" linkages and end with the formation of ether bonds.