AbstractDye‐sensitized solar cells equipped with cationic and neutral RuII‐based sensitizers [Ru(ddpd){tpy(COOH)3}]2+ [12+; ddpd = N,N′‐dimethyl‐N,N′‐di(pyridin‐2‐yl)pyridin‐2,6‐diamine, tpy(COOH)3 = 2,2″6′,2″‐terpyridine‐4,4′,4″‐tricarboxylic acid] and [Ru(ddpd){tpy(COOH)(COO)2}] (2) with and without the coadsorbent chenodeoxycholic acid were constructed with I3–/I– or the CoIII/II‐based redox mediators [Co(bpy)3]3+/2+ (33+/2+; bpy = 2,2′‐bipyridine) and [Co(ddpd)2]3+/2+ (43+/2+) in the presence of LiClO4 and 4‐tert‐butylpyridine. The best photovoltaic performance was achieved by using the 43+/2+ shuttle and the neutral sensitizer 2 without coadsorbent. The higher short‐circuit photocurrent density and higher electron recombination lifetimes obtained with this combination suggest slow electron recombination kinetics at the TiO2 surface with the CoIII complex 43+. The slow electron transfer to 43+ is tentatively ascribed to the high‐lying π* orbitals of the electron‐rich ddpd ligands, which result in a weak electronic coupling. This contrasts with the faster recombination with 33+, which features the low‐energy π* orbitals of the bpy ligands.