In the context of the development of new electron mediators for dye-sensitized solar cells that could efficiently substitute the more common I3(-)/I(-) redox couple, we have prepared a series of Cu(I)- phenanthroline complexes through an easy synthetic route. The novel [Cu(2-mesityl-4,7-dimethyl-1,10-phenanthroline)2]PF6 (3) is of particular interest because the presence of the bulky mesityl groups protects as a kiss lock the Cu center, leading to superior dye regeneration kinetics with respect to simpler phenanthroline-based Cu(I) complexes and to a lower dark current with respect the I3(-)/I(-). The exploitation of a dual-component electrolyte constituted by (3) and a Fe(II) comediator, in combination with the [Ru(4,4'-dicarboxy-2,2'-bipyridine)2(4,4'-dinonyl-2,2'-bipyridine)](PF6)2 sensitizer, allowed us to increase the performance of the cell, reaching Jsc values of 4.0 mA cm(-2), comparable to that recorded with I3(-)/I(-) (3.8 mA cm(-2)).