Bicontinuous mesoporous silica with hierarchical pore structure was obtained by self-assembly approach under biphasic oil-water system. The silica consists of two kinds of interconnecting pores with sizes of ca. 10 nm and ca. 40 nm, and has a surface area of 711 m(2) g(-1). By introducing the synthesized silica as matrix, novel composite gel electrolytes are fabricated, which show high ionic conductivity. The composite gel electrolyte could be used in both dye-sensitized solar cells (DSSCs) and lithium battery. Our results demonstrate that the quasi-solid state DSSC based on the novel composite electrolyte exhibits an encouraging overall efficiency of 4.31% at room temperature, and the lithium battery with sound capacity and capacity retention is also achieved. (C) 2009 Elsevier B.V. All rights reserved.