We report a new concept for the design of metal-free organic dyes (OD5–OD9) with an extended donor–π–acceptor (D–π–A) molecular framework, in which the donor terminal unit is attached by a hole-extending side chain to retard back electron transfer and charge recombination; the π-bridge component contains varied thiophene-based substituents to enhance the light-harvesting ability of the device. The best dye (OD9) has a D–A–π–A configuration with the hexyloxyphenylthiophene (HPT) side chain as a hole-extension component and a benzothiadiazole (BTD) internal acceptor as a π-extension component. The co-sensitization of OD9 with the new porphyrin dye LW24 enhanced the light-harvesting ability to 800 nm; thus, a power conversion efficiency 5.5 % was achieved. Photoinduced absorption (PIA) and transient absorption spectral (TAS) techniques were applied to account for the observed trend of the open-circuit voltage (V_OC) of the devices. This work provides insights into the molecular design, photovoltaic performance, and kinetics of charge recombination.