The combination of beta-substituted Zn2+ porphyrin dyes and copper-based electrolytes represents a sustainable route for economic and environmentally friendly dye-sensitized solar cells. Remarkably, a new copper electrolyte, [Cu(2-mesityl-1,10-phenanthroline)2] (+/2+), exceeds the performance reached by Co2+/3+ and I-/reference electrolytes.