New π-extended porphyrin dyes YD26-YD29 with long alkoxyl chains at the ortho positions of the meso-phenyls, and meta di-tert-butylphenyl-substituted porphyrins YD12-CN, and YD13-CN were synthesized for dye-sensitized solar cells, and their optical, electrochemical and photovoltaic properties were investigated and compared with those of YD12 and YD13. The absorption spectra of YD26-YD29 showed a slight red shift of Soret bands and blue shift of Q bands as compared to the meta-substituted porphyrins due to the electron-donating effects of dioctyloxy substituents at the ortho-positions of the meso-phenyl rings. Replacement of the carboxyl with a cyanoacrylic acid as the anchoring group results in significant broadening and red shifts of the absorptions, which is due to the strong electronic coupling between the pull unit and the porphyrin ring facilitated by the C≡C triple bond. The electrochemical studies and quantum-chemical calculations (DFT) indicated that the ortho alkoxy-substituted sensitizers exhibit lower oxidation potential, i.e. a higher HOMO energy level, and their HOMO-LUMO gaps are comparable to the meta-substituted analogues. The photovoltaic measurements confirmed that the ortho-octyloxy groups in the two meso-phenyls of YD26 and YD27 play a significant role in preventing dye aggregation thereby enhancing the corresponding short-circuit current density and open-circuit voltage. The power conversion efficiency (η) of YD26 is 8.04%, which is 11% higher than that of YD12, whereas the efficiency of YD27 is 6.03%, which is 135% higher than that of YD13. On the other hand, the poor performance of YD28 and YD29 is due to the floppy structural nature and limited molecular rigidity of the cyanoacrylic acid anchor.