Five new thiocyanate-free ruthenium(II) complexes with different electron-donating functionalized cyclometalating ligands C^N were synthesized, characterized and applied as photosensitizers in dye-sensitized solar cells (DSSCs). Their photophysical, electrochemical, thermal and photovoltaic properties have been investigated and density functional theory (DFT) calculations have been carried out on these dyes. These dyes exhibit good thermal stability with the onset decomposition temperature at 5% weight-loss (Td) of around 330 °C. The DSSC device using the Ru(II) dye with the 9-tolylcarbazole chromophore exhibited the highest power conversion efficiency (η) up to 3.39%, with a short-circuit photocurrent density (Jsc) of 8.06 mA cm−2, an open-circuit photovoltage (Voc) of 0.62 V and a high fill factor (ff) of 0.68 under illumination of an AM 1.5 solar cell simulator.Five new thiocyanate-free ruthenium(II) complexes with different electron-donating functionalized cyclometalating ligands C^N were synthesized and characterized by both spectroscopic and theoretical computational methods. These compounds were also used as dyes in the fabrication of dye-sensitized solar cells.Download full-size image