Smectic 1-dodecyl-3-methyl-1H-imidazol-3-ium 1-methyl-1H-tetrazole-5thiolate ([C(12)MIm][T]) has been prepared for dye-sensitized solar cells (DSSCs). The electrolyte consisting of [C(12)MIm][T] and di-5-(1-methyltetrazole) disulfide (T-2) with mole ratio 2:1 exhibited smectic A (S-A) liquid crystal phase over a temperature range from 12.5-75.5 degrees C. A bilayer nanostructure formed in the S-A phase and the T-/T-2 redox couple was intercalated between the smectic layers. Photovoltaic characterization revealed that the power conversion efficiency of the smectic T-/T-2 DSSC increased with the increase in temperature and reached 4.1% at 70 degrees C under simulated AM1.5G solar light. Regression analysis of temperature dependent charge diffusion coefficients and viscosities suggested that the charge transport in the T-/T-2 electrolyte was dominated by the Grotthuss-type exchange reaction. The lamellar nanostructure of T-/T-2 promoted the Grotthuss-type charge transport and improved the DSSC performance. The ordered arrangement of the redox couple offers an effective way to enhance the charge transport for the DSSC electrolytes unfavorable for physical ion diffusion. (C) 2018 Elsevier Ltd. All rights reserved.