Employing a mesoscopic titania photoanode whose bilayer structure was judiciously selected to fit the optoelectronic characteristics of the Ru-based heteroleptic complex Na-cis-Ru(4,4'-(5-hexyltiophen-2-yl)-2,2'-bipyridine)(4-carboxylic-acid-4'-carboxylate-2,2'-bipyridine)(thiocyanate)(2), coded as C101, we investigated the effect of temperature for dye adsorption on the photovoltaic performance of dye-sensitized solar cells (DSCs). We found a significant efficiency enhancement upon lowering the temperature applied during the sensitizer uptake from solution. When the dye adsorption was performed at 4 °C, the photovoltaic performance parameters measured under standard reporting conditions (AM1.5 G sunlight at 1000 W/m(2) intensity and 25 °C), i.e., the open circuit voltage (V(oc)), the short circuit photocurrent density (J(sc)), the fill factor (FF), and consequently the power conversion efficiency (PCE), improved in comparison to cells stained at 20 and 60 °C. Results from electrochemical impedance spectroscopy (EIS) and attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) show that the self-assembled layer of C101 formed at lower temperature impairs the back-electron transfer from the TiO(2) conduction band to the triiodide ions in the electrolyte more strongly than the film produced at 60 °C. Profiting from the favorable influence that the low-temperature dye uptake exerts on photovoltaic performance, we have realized DSCs showing a power conversion efficiency of 11.5%.