We present a time-saving staining protocol based upon the low-toxicity and nonvolatile solvent dimethyl sulfoxide for a high-efficiency dye-sensitized solar cell, which is very critical for the roll-to-roll flexible cell production. Power conversion efficiencies of 11.7-12.1% were achieved under AM1.5G simulated sunlights. The intrinsic roles of lithium cations on efficiency enhancement were scrutinized by measuring transient absorption and electrical impedance spectroscopies. Our studies have revealed that lithium ions can enhance exciton dissociation at the energy-offset dye/titania interface effectively. Charge collection is not found to be a crucial current loss channel in our high-efficiency dye-sensitized solar cell.