A novel ionic liquid crystal (ILC) system (C18IMCNBr) with a liquid crystal alignment used as an electrolyte for a dye-sensitized solar cell (DSSC) showed the higher short-circuit current density (Jsc) and the higher light-to-electricity conversion efficiency than the system using the non- alignment liquid crystalline ionic liquid (C18IMCNBr),due to the higher conductivity of liquid crystal alignment. The larger Jsc and efficiency value of liquid crystal alignment supported that the higher conductivity of liquid crystal alignment is attributed to the enhancement of the exchange reaction between iodide species. As a result of formation of the two-dimensional electron conductive pathways organized by the localized I3- and I- at liquid crystal alignment layers, the concentration of polyiodide species exemplified by Im- (m =5,7, ...) was higher in alignment C18IMCNBr. However, in the two-dimensional electron conductive pathways of C18IMCNBr, more collision frequencies between iodide species (I-,I3-, and Im-) could be achieved than that in the three-dimensional space of C18IMCNBr, which could lead to the promotion of the exchange reaction between iodide species, the contribution of a two-dimensional structure of the conductive pathway through the increase of collision frequency between iodide species was proposed.