In organic electronics, aromatic fused-ring is the basic unit that provides π-electrons to construct solution-processable, lightweight, flexible semiconductors and governs the device performance in a wide range of new technologies. The main challenge on developing new π-skeletons for tuning the material properties is the limitation of available chemical approach. Herein, we addressed the problems on chemical synthesis and for the first time successfully synthesized two pentacyclic siloxy-bridged π-conjugated isomers (SiO5T-5 & SiO5T-10), for investigating the synergistic effects of Si and O atoms on the geometric and electronic influence of the π-units in organic electronics. Notably, the synthesis routes for both of SiO5T-5 and SiO5T-10 possess several advantages over the previous approaches for delivering conventional aromatic fused-ring such as environmentally benign tin-free synthesis, and less synthetic steps. To explore its potential application as photovoltaic materials, two isomeric A-D-A acceptors based on these two SiO5Ts isomers were developed, showing a decent device efficiency of 10%, which is higher than those of carbon and carbon-oxygen analogue-based PSCs. Our study indicates that the siloxy-bridged π-conjugated system is a potential donor core for photovoltaic materials. The silicon and oxygen synergistic effects presented herein would bring new vigor and vitality for further improving the performance of organic solar cells.