Two new ullazine-based organic dyes have been synthesized for applications in nanocrystalline TiO2-based dye-sensitized solar cells (DSSCs). Overall conversion efficiencies up to 3.63% were obtained for DSSCs based on these dyes. The dye with a tert-butyl antenna exhibited a higher and redshifted absorption pattern resulting in increased light-harvesting property. Compared to the unsubstituted dye, the photocurrent density, open-circuit photovoltage and overall power conversion efficiency (PCE) of solar cells based on the tert-butyl substituted dye are improved. The decreased PCE of the solar cell based on unsubstituted dye results mainly from the increased recombination rate and decreased electron lifetime, as evidenced from impedance and photovoltage decay measurements. Density functional theory (DFT) and time-dependent DFT calculations were performed to predict the geometries, electronic structure, and the optical and electrochemical properties of the dyes.