A new compound, LiI(3-hydroxypropionitrile)(2), is reported here. According to its single-crystal structure (C2/c), this compound has 3-D transporting paths for iodine. Further ab initio calculation shows that the activation energy for diffusion of iodine (0.73 eV) is much lower than that of lithium ion (8.39 eV) within the lattice. Such a mono-ion transport feature is favorable as solid electrolyte to replace conventional volatile organic liquid electrolytes used in dye-sensitized solar cells (DSSC). LiI and 3-hydroxypropionitrile (HPN) can form a series of solid electrolytes. The highest ambient conductivity is 1.4 x 10(-)(3) S/cm achieved for LiI(HPN)(4). However, it tends to form large crystallites and leads to poor filling and contact within porous TiO(2) electrodes in DSSC. Such a drawback can be greatly improved by introducing micrometer-sized and nanosized SiO(2) particles into the solid electrolyte. It is helpful not only in enhancing the conductivity but also in improving the interfacial contact greatly. Consequently, the light-to-electricity conversion efficiency of 5.4% of a DSSC using LiI(HPN)(4)/15 wt % nano-SiO(2) was achieved under AM 1.5 simulated solar light illumination. Due to the low cost, easy fabrication, and relatively high conversion efficiency, the DSSC based on this new solid-state composite electrolyte is promising for practical applications.