New opp-dibenzoporphyrins were prepared in a concise method that was based on a Pd0-catalyzed cascade reaction. These porphyrins, which contained carboxylic-acid linker groups on benzene rings that were fused to the porphyrin at their β,β′-positions, were examined as sensitizers for dye-sensitized solar cells for the first time. Whereas all of the porphyrins showed solar-energy-to-electricity conversion, an opp-dibenzoporphyrin with conjugated carboxylic-acid linkers displayed the highest conversion efficiency and an exceptionally high Jsc value. Cyclic voltammetry of these porphyrins suggested that the fusion of two aromatic benzene rings onto the periphery of the porphyrin lowered the HOMO–LUMO energy gap; the incorporation of a conjugated carboxylic-acid linker group decreased the HOMO–LUMO gap even further. These CV data are consistent with DFT calculations for these porphyrins and agree well with the UV/Vis absorption- and fluorescence spectra of these porphyrins.