Dye‐sensitized solar cells (DSSCs) based on Cu^II/I bipyridyl or phenanthroline complexes as redox shuttles have achieved very high open‐circuit voltages (V_OC, more than 1 V). However, their short‐circuit photocurrent density (J_SC) has remained modest. Increasing the J_SC is expected to extend the spectral response of sensitizers to the red or NIR region while maintaining efficient electron injection in the mesoscopic TiO₂ film and fast regeneration by the Cu^I complex. Herein, we report two new D‐A‐π‐A‐featured sensitizers termed HY63 and HY64, which employ benzothiadiazole (BT) or phenanthrene‐fused‐quinoxaline (PFQ), respectively, as the auxiliary electron‐withdrawing acceptor moiety. Despite their very similar energy levels and absorption onsets, HY64‐based DSSCs outperform their HY63 counterparts, achieving a power conversion efficiency (PCE) of 12.5 %. PFQ is superior to BT in reducing charge recombination resulting in the near‐quantitative collection of photogenerated charge carriers.