The option of using conjugated π-linkers is critical for rational molecular design toward an energy-level strategy for organic sensitizers. To further optimize photovoltaic performance, methyl- and octyl-substituted 4H-cyclopenta[2,1-b:3,4-b']dithiophene (CPDT) are introduced into D-A-π-A featured sensitizers. Along with CPDT, instead of thiophene as conjugated bridge, WS-39 and WS-43 exhibit an extended spectral response due to the excellent conjugation and coplanarity of CPDT. Specifically, we focused on the critical effect of length of the alkyl group linked to the bridging carbon atoms of CPDT on the photovoltaic performances. Octyl-substituted WS-39 shows a broader IPCE onset with an enhanced photovoltage relative to the analogue WS-5. In contrast, WS-43, with methyl substituted on the CPDT moiety, presents a relatively low quantum conversion efficiency within the whole spectral response region, along with low photocurrent density. WS-43 displays a distinctly low IPCE platform, predominately arising from the short electron diffusion length with significant electron loss during the electron transport. The relative movement of the conduction band edge (E(CB)) and charge transfer resistance as well as lifetime of injected electrons are studied in detail. Under standard AM 1.5 conditions, WS-39-based solar cells show a promising photovoltaic efficiency of 9.07% (J(SC) = 16.61 mA cm(-2), V(OC) = 770 mV, FF = 0.71). The octyl chains attached on CPDT can provide dual protection and exhibit a high propensity to prevent binding of the iodide-triiodide redox couple, producing an efficient shielding effect to retard the charge recombination and resulting in improvement of V(OC). Our research paves the way to explore more efficient sensitizers through ingenious molecular engineering.