This work identifies the dithiafulvenyl unit as an excellent electron donor for constructing D?π–A-type metal-free organic sensitizers of dye-sensitized solar cells (DSCs). Synthesized and tested are three sensitizers all with this donor and a cyanoacrylic acid acceptor but differing in the phenyl (DTF-C1), biphenyl (DTF-C2), and phenyl–thiopheneyl–phenyl π-bridges (DTF-C3). Devices based on these dyes exhibit a dramatically improved performance with the increasing π-bridge length, culminating with DTF-C3 in η = 8.29% under standard global AM 1.5 illumination.