Recently, dye-sensitized solar cell (DSSC) has attracted the attention of research worldwide and become a low-cost solar cell with highest efficiencies exceeding 11%. To date, many works have been devoted to improve the efficiencies of DSSC by both materials and electrical approach. Our (TD)DFT-based procedure made it possible to get insights into the geometrical and electronic structures of the dyes and to unravel the structural modifications optimizing the properties of Catechol-based DSSC. We try to explain the electron injection pathways of Catechol (Cat), (pyridin-4-yl)vinyl and (quinolinyl)vinyl to Catechol (known as Cat-v-P and Cat-v-Q) bound to TiO2 cluster and explain the role of Quinonine and Pyridine, as electron donor, to Catechol which contribute to increase the quality factor of the cell. (C) 2011 Elsevier Ltd. All rights reserved.