Robust radical-substituted polymers with ideal redox capability were used as "command surfaces" for liquid crystal orientation. The alignment of the smectic liquid crystal electrolytes with low-dimensional ion conduction pathways was reversible and readily switched hi response to the redox states of the polymers. In one example, a charge storage device with a cooperative redox effect was fabricated. The bulk ionic conductivity of the cell was significantly decreased only after the electrode was fully charged, due to the anisotropic ionic conductivity of the electrolytes (ratio >10(3)). The switching enabled both a rapid cell response and long charge retention. Such a cooperative Command surface of-self-assembled structures Will give rise to new highly energy efficient supramolecular-based devices including batteries, charge carriers, and actuators.