Four D–A–π–A motif organic sensitizers (IQ9, IQ10, IQ11 and IQ12) in the absence or presence of thiophene substituents grafted onto the auxiliary acceptor of a quinoxaline unit have been developed for dye sensitized solar cells (DSSCs). Upon changing the π-linker from benzene to thiophene, the photocurrent (Jsc) of IQ10 increases around 2-fold, and the photovoltage (Voc) decreases by 52 mV compared to that of IQ9. It is attributed to the fact that compared with the benzene linker, the thiophene conjugated bridge in dye IQ10 induces a small twist in the molecular planarity, thus resulting in the high light-harvesting capability (beneficial to Jsc) and high charge recombination (unbeneficial to Voc). To prevent this “trade-off” effect between photocurrent and photovoltage, the building block of 2,3-dithienylquinoxaline as an auxiliary unit is specifically incorporated, which brings forth several advantages such as distinctly extending the light-harvesting region, increasing molar absorption coefficients, and blocking the dye self-aggregation to reduce charge recombination. Remarkably, dye IQ12 exhibits a beneficial balance between Jsc (17.97 mA cm−2) and Voc (715 mV), along with a promising photovoltaic efficiency of 8.76%, much better than the corresponding dyes IQ9 (2.91%), IQ10 (7.75%) and IQ11 (6.56%). As demonstrated, the two twisted thiophene groups grafted onto the quinoxaline unit facilitate the resulting compact sensitizer layer to effectively overcome the charge recombination drawbacks in Voc arising from the thiophene π-bridge linker, providing a rational molecular engineering to pursue the synergistic enhancement in the photocurrent and photovoltage for highly efficient organic sensitizers.