The photovoltaic performance of dye-sensitized solar cells (DSSCs) is enhanced by modifying the binary room temperature ionic liquid (RTIL) electrolyte with additives and iodine. The average photoelectric conversion efficiency (PCE) of 6.39% is achieved. Through electrochemical impedance spectroscopy (EIS), cyclic voltammetry scans and incident photon-to-current conversion efficiency (IPCE) data, the working principles are analyzed. The enhancement is mainly attributed to the improvement of short circuit current which is caused by the reduction of overall internal resistance of the devices. Durability tests are measured at room temperature, and the long-term stability performance can be maintained.