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In recent years, copper redox mediators have attracted growing interest in dye-sensitized solar cells (DSCs). However, experiments revealed that ubiquitously used Lewis-base additives in the electrolytes coordinate to the CuII species, which restricts further enhancement of device performance and stability. We report the application of copper complexes endowed with diamine-tripyridine pentadentate ligands, [Cu(tpe)]2+/+ (tpe=N-benzyl-N,N',N'-tris(pyridin-2-ylmethyl)ethylenediamine) and [Cu(tme)]2+/+ (tme=N-benzyl-N,N',N'-tris(6-methylpyridi