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In this article, the unique bristled silver nanowires@TiO 2 core–shell nanostructure (AgNW@TiO 2 ) is introduced into the TiO 2 photoanode and applied to assemble dye-sensitized solar cells (DSSCs). The effects of the “optics–electrics highways” composites on the photovoltaic and photocatalytic behaviors of DSSCs are investigated in detail. Experiment research and FDTD simulation indicate that both the localized surface plasmon resonance (LSPR) and plasmonic waveguide effect could enhance light harvesting efficiency. By electrical properties and electrochemical analysis, it is demonstrated that the AgNW@TiO 2 significantly accelerates electron transport as well as reduces recombination, then the charge collection efficiency of DSSCs is improved. The composite-modified DSSC exhibits the best performance with the power conversion efficiency of 8.84% which is superior to that of the free–modified DSSC with the PCE of 6.16%. [ABSTRACT FROM AUTHOR]