Molecularly ordered composites of polyvinylimidazole-[Os(bipyridine) 2Cl] (PVI-[Os(bpy) 2Cl]) and glucose oxidase (GOD) are assembled inside a film of aligned carbon nanotubes. The structure of the prepared GOD/PVI-[Os(bpy) 2Cl]/CNT composite film is entirely uniform and stable; more than 90% bioelectrocatalytic activity could be maintained even after storage for 6 days. Owing to the ideal positional relationship achieved between enzyme, mediator and electrode, the prepared film shows a high bioelectrocatalytic activity for glucose oxidation (ca. 15 mA cm-2 at 25 °C) with an extremely high electron turnover rate (ca. 650 s -1) comparable to the value for the GOD solutions, indicating almost every enzyme molecules entrapped within the ensemble (ca. 3 × 10 12 enzymes in a 1× 1 mm2 film) can work to the full. The free-standing, flexible composite film can be used by winding on a needle device, for example, a self-powered sugar monitor.