This paper firstly reports the effect of deoxyribonucleic acid ( DNA) molecules extracted from chickpea and wheat plants on the injection/recombination of photogenerated electrons and sensitizing ability of dye-sensitized solar cells (DSSCs). These high-yield DNA molecules are applied as both linker bridging unit as well as thin tunneling barrier (TTB) at titanium dioxide (TiO2)/dye interface, to build up high-efficient DSSCs. With its favorable energy levels, effective linker bridging role, and double helix structure, bifunctional DNA modifier shows an efficient electron injection, suppressed charge recombination, longer electron lifetime, and higher light harvesting efficiency, which leads to higher photovoltaic performance. In particular, a photoconversion efficiency (PCE) of 9.23% is achieved by the binary chickpea and wheat DNA-modified TiO2 (CW@TiO2) photoanode. Furthermore, time-resolved fluorescence spectroscopy measurements confirm a better electron transfer kinetics for DNA-modified TiO2 photoanodes, implying a higher electron transfer rate (k(ET)). This work highlights a great contribution for the photoanodes that are linked with DNA molecule, which act as both bridging unit and TTB to control the charge recombination and injection dynamics, and hence, boost the photovoltaic performance in the DSSCs.