Two series dyes of azo-bridged zinc porphyrins have been devised, synthesized, and performed in dye-sensitized solar cells, in which salicylic acids and azo groups were introduced as a new anchoring group and π-conjugated bridge via a simple synthetic procedure. The representation of the new dyes has been investigated by optical, photovoltaic, and electrochemical means. The photoelectric conversion efficiency of their DSSC devices has been improved compared with other DSSC devices sensitized by symmetrical porphyrin dyes. The results revealed that tridentate binding modes between salicylic acid and TiO2 nanoparticles could enhance the efficiency of electron injection. The binding modes between salicylic acid and TiO2 nanoparticles may play a crucial role in the photovoltaic performance of DSSCs.