A novel thiocyanate-free cyclometalleted ruthenium sensitizer for solar cells is designed and developed. Upon anchoring to nanocrystalline TiO2 films, it exhibits a remarkable incident monochromatic photon-to-current conversion efficiency of 83%. The solar cell employing a liquid-based electrolyte exhibits a short circuit photocurrent density of 17 mA/cm(2), an open circuit voltage of 800 mV, and a fill factor of 0.74, corresponding to an overall conversion efficiency of 10.1% at standard AM 1.5 sunlight. To understand the structural, electronic, and optical properties of the cyclometalleted ruthenium sensitizer, we have investigated using density functional theory (DFT) and time-dependent DFT (TDDFT). Our results show the HOMO is located mostly on ruthenium and cyclometalated ligand, while the LUMO is on 4-carboxylic acid-4'-carboxylate-2,2'-bipyridine. Molecular orbitals analysis confirmed the experimental assignment of redox potentials, and TDDFT calculations allowed assignment of the visible absorption bands. The present findings provide new design criteria for the next generation of ruthenium sensitizers and help foster widespread interest in the engineering of new sensitizers that interact effectively with the I-/I-3(-) redox couple.