Dye-sensitized solar cells (DSSCs) based on organic dyes adsorbed on TiO2 electrodes, which emerged as a new generation of sustainable photovoltaic devices, have received considerable attention because of high incident solar light-to-electricity conversion efficiency and low cost of production. The aim of this Highlight Review is to indicate the importance of creating effective D-pi-A dye sensitizers capable of controlling not only photophysical and electrochemical properties of the dyes themselves but also molecular arrangement and/or orientation of the dyes on TiO2 surface to provide a good electron communication between the dye and TiO2 electrode, for developing high-performance DSSCs.