It is shown that an ionic dye Y can be electrostatically bonded to an ionic molecule X of opposite charge anchored to a TiO2 surface via suitable ligands. Dye-sensitized solid-state photovoltaic cells of the configuration n-TiO2/X-Y/p-CuSCN were constructed with X = trihydroxybenzoic acid or mercurochrome and Y = methyl violet. Cells of this configuration were found to be more efficient and delivered higher short-circuit photocurrents and open-circuit photovoltages compared to the cells based only on methyl violet or mercurochrome. It is suggested that this technique would be a means of extending the spectral response of dye-sensitized photovoltaic devices. The formation of a wider barrier by coupling of anionic and cationic species also improves the cell performance by suppression of recombination.