Abstract The present work aimed to find the answer how does the isomerization of the Ru based dyes affect the overall photon-to-current efficiency of the DSSCs and to explain the charge transfer phenomenon occurring on the dye/nanosemiconductor interface. Therefore, electronic and optical properties of three bipyridine derivatives anchored on the TiO2 electrode were investigated by computational simulations based on quantum chemistry codes performed on a cluster model and the predictions compared with experimental responses. The quantum chemical calculations carried out for the para-, meta- and ortho-isomers has given the possibility to explain the role of an anchor group position in the DSSC devices design. An in-depth analysis of the obtained data shows that the nature of the bonding between the anchor groups and the semiconducting nanoparticles affects the charge transfer at the interfaces. The electronic properties obtained for the hybrid systems and their components indicate that solar cells with the para-derivatives of the Ru based dyes as sensitizers exhibit the highest photo conversion efficiency. The observed phenomenon was explained based on the photogenerated excitons in the organic groups and their dissociation at the dye/semiconductor interfaces to ensure the free charge carriers.