Four organic D–A–π-A-featured sensitizers (TQ1, TQ2, IQ1, and IQ2) have been studied for high-efficiency dye-sensitized solar cells (DSSCs). We employed an indoline or a triphenylamine unit as the donor, cyanoacetic acid as the acceptor/anchor, and a thiophene moiety as the conjugation bridge. Additionally, an electron-withdrawing quinoxaline unit was incorporated between the donor and the π-conjugation unit. These sensitizers show an additional absorption band covering the broad visible range in solution. The contribution from the incorporated quinoxaline was investigated theoretically by using DFT and time-dependent DFT. The incorporated low-band-gap quinoxaline unit as an auxiliary acceptor has several merits, such as decreasing the band gap, optimizing the energy levels, and realizing a facile structural modification on several positions in the quinoxaline unit. As demonstrated, the observed additional absorption band is favorable to the photon-to-electron conversion because it corresponds to the efficient electron transitions to the LUMO orbital. Electrochemical impedance spectroscopy (EIS) Bode plots reveal that the replacement of a methoxy group with an octyloxy group can increase the injection electron lifetime by a factor of 2.4. IQ2 and TQ2 can perform well without any co-adsorbent, successfully suppress the charge recombination from TiO2 conduction band to I3− in the electrolyte, and enhance the electron lifetime, resulting in a decreased dark current and enhanced open circuit voltage (Voc) values. By using a liquid electrolyte, DSSCs based on dye IQ2 exhibited a broad incident photon-to-current conversion efficiency (IPCE) action spectrum and high efficiency (η=8.50 %) with a short circuit current density (Jsc) of 15.65 mA cm−2, a Voc value of 776 mV, a fill factor (FF) of 0.70 under AM 1.5 illumination (100 mW cm−2). Moreover, the overall efficiency remained at 97 % of the initial value after 1000 h of visible-light soaking.