Redox-active phenazinium salts bonded to amphiphilic polymer backbones are demonstrated to function as high-performance electron-transfer mediators in enzymatic bioanodes applicable to biofuel cells. The redox-active moieties could be easily tethered to the electrodes by physical adsorption of the hydrophobic regions of the polymer backbones onto the electrode surface. On the other hand, long hydrophilic chains were essential to ensure high mobility of the redox-active moieties in aqueous solutions and to enhance their electron-transfer properties. We found that an amphiphilic mediator with a linear polymer backbone exhibited stable adsorption behavior on the electrode surface and generated high bioelectrocatalytic current (>1.8 +/- 0.32 mA/cm(2)) in the presence of pyrroloquinoline quinone-dependent glucose dehydrogenase and an aqueous solution of glucose fuel. This current was more than two times higher than that of an electrode treated with a low-molecular-weight phenazinium salt. Moreover, the bioelectrode modified with the polymer mediator retained the high electrocatalytic current after 10 exchanges of the glucose fuel. The mediator-modified bioelectrodes are expected to be useful for various bio-related energy and electronic devices.