摘要： Due to the role of dye in dye-sensitized solar cells (DSSCs), design novel dye sensitizer is effective strategy to improve power conversion efficiency. To this end, the fundamental issue is the understanding sensitizer’s trilateral relationship among molecular structure, optoelectronic properties and photovoltaic performance. Here, on the one hand, to investigate the relationship between molecular structure and properties, considering the good performance of N-annulated perlyene dye sensitizers, the geometries, electronic structures and excitations of the selected representative organic dye sensitizers C276, C277, C278 and the dyes adsorbed on TiO2 clusters were calculated. It is found that, fusing thienyl to N-annulated perlyene can elevate the highest occupied molecular orbital (HOMO) energies, reduce orbital energy gap, increase density of states, expand HOMO to benzothiadiazole moiety, enhance charge transfer excitation, elongate fluorescence lifetime, amplify light harvesting efficiency and induce red-shift of absorption spectra. The transition configurations and molecular orbitals of dye adsorbed systems support that the electron injection in DSSCs based on these dyes are fast mode. On the other hand, to exposure the relationship between properties and performance, based upon extensive analysis of electronic structures and excitation properties of these dye sensitizers and the dye adsorbed systems, we present new quantities as open-circuit voltage and short-circuit current density descriptors, which celebrate the quantitative bridge between the photovoltaic parameters and the electronic structure related properties. The results of this work are critical for design novel dye sensitizers for solar cells.